CN111479878A - Leuco colorants and compositions - Google Patents

Abstract

The present invention relates to a leuco composition comprising at least one leuco compound comprising a leuco moiety and a polyalkylene oxide moiety covalently bonded to the leuco moiety. The polyalkylene oxide moiety contains at least one ethylene oxide group and at least one propylene oxide group. The present invention also relates to a laundry care composition comprising (a) at least one laundry care ingredient and (b) a leuco composition as described above. The present invention additionally relates to a method of treating textiles, said method comprising the steps of: (a) providing said laundry care composition; (b) adding said laundry care composition to a liquid medium; (c) adding said laundry care composition to a liquid medium; The textile is placed in the liquid medium; (d) optionally, the textile is rinsed; and (e) the textile is dried.

Description

Leuco colorants and compositions

technical field

This application describes leuco compositions, laundry care compositions containing the leuco compositions, and the use of these compositions in the laundering of textiles. These types of compositions are provided in a stable, substantially colorless state, which can then be converted to intense after exposure to certain physical or chemical changes (eg, exposure to oxygen, ion addition, exposure to light, etc.). Intense colored state. Laundry care compositions comprising leuco compounds are designed to enhance the apparent or visually perceptible whiteness of textiles washed or otherwise treated with the laundry care composition, or to impart a desired hue to said textiles.

Background technique

As textile substrates age, their color tends to fade or yellow due to exposure to light, air, dirt, and natural degradation of the fibers that make up the substrate. Accordingly, in order to visually enhance these textile substrates and counteract fading and yellowing, it has become known in the art to use polymeric colorants to color consumer products. For example, the use of brighteners (or optical brighteners or bluing agents) in textile applications is well known. However, traditional whiteners tend to lose efficacy on storage due to deleterious interactions with other formulation components, such as fragrances. In addition, such brighteners may deposit poorly on textile substrates. As a result, formulators tend to increase the level of brightener to offset any loss of efficacy on storage and/or increase the amount of brightener available for deposition on textile substrates.

It is also known in the art that leuco dyes exhibit a change from a colorless or lightly colored state to a colored state upon exposure to certain chemical or physical triggers. The coloration changes that occur are usually visually perceptible to the human eye. Many of these compounds have a certain absorbance in the visible region (400-750 nm), and thus have a more or less certain color. In the present invention, a dye is considered to be a "leuco dye" if it does not exhibit significant color at its application concentration and conditions, but does in its triggered form. The color change upon triggering results from the molar decay coefficient of the leuco dye molecule in the range of 400-750 nm, preferably in the range of 500-650 nm, and most preferably in the range of 530-620 nm (also referred to in some literature as molar extinction coefficient, molar absorptivity and/or molar absorptivity). The increase in molar decay coefficient of the leuco dye before and after triggering should be greater than 50%, more preferably greater than 200%, and most preferably greater than 500%.

Leuco compounds can be used as brighteners in laundry care compositions such as laundry detergents. In such applications, the addition of the leuco compound in an unpigmented or only slightly pigmented state does not significantly affect the aesthetics of the laundry care composition. The leuco compound can then be converted to a colored state where it imparts the desired whitening benefit to the textile substrate.

One of the challenges in achieving whiteness benefits through the use of hueing technology is that consumers typically have clothing that is expected to be lightly tinted (eg, pinkish yellow), and hueing agents, shade modifiers ( The application of shading agents) or bluing agents can compromise the intended color of such garments, resulting in consumer dissatisfaction. There remains a need to develop methods of adjusting hue that selectively deposit on aged consumer cotton garments (those most likely to yellow over time, where the yellowing requires color correction), and Does not deposit well on fresh clean cotton clothing that does not require color correction.

While many leuco colorants show a preference for deposition on aged cotton garments obtained from consumers over fresh clean cotton, we found that with propoxylated groups ( Substitution of certain ethoxylated derivatives of TAM dyes by propoxylategroups resulted in improved bias. These leuco colorants having both EO oxyalkylene groups and PO oxyalkylene groups show greater bias than those having only EO oxyalkylene units. Thus, the leuco colorants of the present invention are better able to provide whitening benefits where needed and avoid the toning of new, clean cotton garments, where such adjusted tones are likely to be considered undesirable.

SUMMARY OF THE INVENTION

In a first embodiment, the present invention provides a leuco composition comprising at least one leuco compound comprising a leuco moiety and an alkylene oxide covalently bound to the leuco moiety moiety, wherein the alkylene oxide moiety comprises at least one ethylene oxide group and at least one propylene oxide group.

In a second embodiment, the present invention provides a laundry care composition comprising (a) at least one laundry care ingredient and (b) a leuco composition as described above.

In a third embodiment, the present invention provides a method of treating textiles, the method comprising the steps of: (a) providing a laundry care composition as described herein; (b) adding the laundry care composition to a in a liquid medium; (c) placing the textile in the liquid medium; (d) optionally, rinsing the textile; and (e) drying the textile.

In a fourth embodiment, the present invention provides a laundry care composition comprising a laundry care ingredient and the leuco composition described herein. In one aspect, the present invention provides a laundry care composition comprising: (i) 2% to 70% by weight of a surfactant; and (ii) 0.0001% to 20.0% by weight of a surfactant as described herein Invisible composition.

In a fifth embodiment, the present invention provides a method of treating textiles, the method comprising the steps of: (a) providing a laundry care composition comprising a leuco composition as described herein, (b) applying the The laundry care composition is added to a liquid medium; (c) the textile is placed in the liquid medium; (d) optionally, the textile is rinsed; and (e) the textile is dried.

Detailed ways

definition

As used herein, the term "alkoxy" is intended to include _C1 - _C8 alkoxy and alkoxy derivatives of polyols having repeating units such as butylene oxide, glycidyl oxide (glycidol oxide), ethylene oxide or propylene oxide.

As used herein, the interchangeable terms "alkylene oxide" and "oxyalkylene", and the interchangeable terms "polyalkylene oxide" and "polyoxyalkylene", respectively, generally refer to compounds containing one or more than one Molecular structure of the following repeating units: -C ₂ H ₄ O-, -C ₃ H ₆ O-, -C ₄ H ₈ O- and any combination thereof. Non _{- limiting} structures corresponding to these groups include, for _example , _-CH2CH2O- , _-CH2CH2CH2O- , _{-CH2CH2CH2CH2O- , -CH2CH ( CH3 )} O- and -CH2CH( _{CH2CH3 ) O-} . Furthermore, the polyoxyalkylene component may be selected from one or more monomers selected from _C2-20 alkylene oxides, glycidyl groups, or mixtures thereof.

The terms "ethylene oxide", "propylene oxide" and "butylene oxide" may be referred to herein by their typical designations "EO", "PO" and "BO", respectively.

As used herein, the terms "alkyl" and "alkyl terminated" are intended to mean any monovalent group formed by removal of a hydrogen atom from a substituted or unsubstituted hydrocarbon. Non-limiting examples include branched or unbranched, substituted or unsubstituted hydrocarbyl moieties, including _C1 - _C18 alkyl, and in one aspect _C1 - _C6 alkyl.

As used herein, unless otherwise indicated, the term "aryl" is intended to include C3 _{- C12} aryl groups. The term "aryl" refers to carbocyclic aryl groups and heterocyclic aryl groups.

As used herein, the term "alkaryl" refers to any alkyl-substituted aryl substituents and aryl-substituted alkyl substituents. More specifically, the term means _C7-16 alkyl substituted aryl substituents and _C7-16 aryl substituted alkyl substituents, which may or may not contain additional substituents.

As used herein, the term "detergent composition" is a subset of laundry care compositions and includes cleaning compositions including, but not limited to, products for laundering fabrics. Such compositions may be pretreatment compositions used prior to the wash step, or may be rinse added compositions, as well as cleaning aids such as bleach additives and "stain-stick" or pretreatment types.

As used herein, unless otherwise indicated, the term "laundry care composition" includes granular, powder, liquid, gel, paste, unit dose, bar and/or tablet detergent and/or fabric treatment compositions, including But not limited to products for laundering fabrics, fabric softening compositions, fabric enhancing compositions, fabric refreshing compositions, and other products for fabric care and maintenance, and combinations thereof. Such compositions may be pretreatment compositions used prior to the washing step, or may be rinse added compositions, as well as cleaning aids such as bleach additives and/or "stain removal sticks" or pretreatment compositions or substrate loadings Substrate-laden products such as dryer added sheets.

As used herein, the term "leuco" (as used in reference to, eg, a compound, moiety, group, dye, monomer, fragment or polymer) refers to an entity (eg, an organic compound or portion thereof) that is After exposure to a specific chemical or physical trigger, undergoes one or more chemical and/or physical changes resulting in a transition from a first color state (eg, unpigmented or substantially colorless) to a second, more highly pigmented state (more highly colored) state. Suitable chemical or physical triggering conditions include, but are not limited to, oxidation, pH changes, temperature changes, and changes in exposure to electromagnetic radiation (eg, light). Suitable chemical or physical changes that occur in leuco entities include, but are not limited to, oxidative and non-oxidative changes such as intramolecular cyclization. Thus, in one aspect, a suitable leuco entity may be the reversibly reduced form of the chromophore. In one aspect, the leuco moiety preferably comprises at least first and second [pi]-systems that are capable of being converted into a combination of said first and The third binding conjugated pi-system of the second pi-system.

As used herein, the term "leuco composition" or "leuco colorant composition" refers to a composition comprising at least two leuco compounds having independently selected structures, as further described herein Detailed Description.

As used herein, the "average molecular weight" of a leuco colorant is reported as a weight average molecular weight, as determined by its molecular weight distribution: As a result of their manufacturing process, the leuco colorants disclosed herein may contain repeating units in their polymer portion Distribution.

As used herein, the terms "maximum extinction coefficient" and "maximum molar extinction coefficient" are intended to describe the molar extinction coefficient at the wavelength of maximum absorption (also referred to herein as the maximum wavelength) in the range of 400 nanometers to 750 nanometers.

As used herein, the term "first color" is used to refer to the color of the laundry care composition prior to triggering, and is intended to include any color, including colorless and substantially colorless.

As used herein, the term "second color" is used to refer to the color of the laundry care composition after triggering, and is intended to include distinguishable from the first color of the laundry care composition by visual inspection or using analytical techniques such as spectrophotometric analysis of any color.

As used herein, the term "transforming agent" refers to any oxidizing agent known in the art other than molecular oxygen in any of its known forms (singlet and triplet).

As used herein, the term "trigger" refers to a reactant suitable for converting a leuco composition from a colorless or substantially colorless state to a colored state.

As used herein, the term "brightener" refers to a dye or leuco colorant that, once triggered, forms a dye that when on white cotton The cloth is shaded with a relative hue angle of 210 to 345, or even a relative hue angle of 240 to 320, or even a relative hue angle of 250 to 300 (eg, 250 to 290).

As used herein, "cellulose substrate" is intended to include any substrate comprising at least a substantial portion by weight of cellulose. Cellulose may be found in wood, cotton, flax, jute, and hemp. Cellulosic matrices can be in the form of powders, fibers, pulps, and articles formed from powders, fibers, and pulps. Cellulosic fibers include, but are not limited to, cotton, rayon (regenerated cellulose), acetate (cellulose acetate), triacetate (cellulose triacetate), and mixtures thereof. Articles formed from cellulosic fibers include textile articles such as fabrics. Articles formed from pulp include paper.

As used herein, articles such as "a" and "an" when used in the claims should be understood to mean one or more or one or more of what is claimed or described.

As used herein, the terms "including" and "comprising" are non-limiting.

As used herein, the term "solid" includes granular, powder, bar and tablet product forms.

As used herein, the term "fluid" includes liquid, gel, paste and gaseous product forms.

Corresponding values for the parameters of Applicants' invention should be determined using the test methods disclosed in the Test Methods section of this application.

Unless otherwise specified, all component or composition levels refer to the active portion of that component or composition and do not include impurities, such as residues, that may be present in commercially available sources of such components or compositions solvent or by-product.

All percentages and ratios are by weight unless otherwise stated. All percentages and ratios are calculated based on the total composition unless otherwise stated.

In one aspect, the molar extinction coefficient of the second colored state at the maximum absorbance in the wavelength range of 200 nm to 1,000 nm (more preferably, 400 nm to 750 nm) is the maximum of the first colored state in the second colored state The molar extinction coefficient at the wavelength of the absorbance is preferably at least 5 times, more preferably 10 times, even more preferably 25 times, most preferably at least 50 times. Preferably, the molar extinction coefficient of the second colored state at the maximum absorbance in the wavelength range of 200 nm to 1,000 nm (more preferably, 400 nm to 750 nm) is the maximum molar extinction coefficient of the first colored state in the corresponding wavelength range At least 5 times, preferably 10 times, even more preferably 25 times, most preferably at least 50 times the extinction coefficient. Those of ordinary skill will realize that these ratios may be much higher. For example, the first color state may have a maximum molar extinction coefficient as small as 10M ^-1 cm ^-1 in the wavelength range of 400nm to 750nm, and the second color state may have as high as 80,000M in the wavelength range of 400nm to 750nm Maximum molar extinction coefficient of ^-1 cm ^-1 or higher, in which case the ratio of extinction coefficients is 8000:1 or higher.

In one aspect, the maximum molar extinction coefficient of the first color state at wavelengths in the range of 400 nm to 750 nm is less than 1000 M ⁻¹ cm ⁻¹ , and the second color state has a maximum molar extinction coefficient at wavelengths in the range of 400 nm to 750 nm. The maximum molar extinction coefficient is greater than 5000 M ^-1 cm ^-1 , preferably greater than 10000 M ^-1 cm ^-1 , 25000 M ^-1 cm ^-1 , 50000 M ^-1 cm ^-1 or even 100000 M ^-1 cm ^-1 . Those skilled in the art will recognize and appreciate that polymers comprising more than one leuco moiety may have significantly higher maximum molar extinction coefficients in the first color state (e.g., due to the additive effect of multiple leuco moieties). Or there are one or more leuco-colored parts that transition into a second colored state).

The present invention relates to a class of leuco colorants useful in laundry care compositions, such as liquid laundry detergents, to provide a blue hue to whiten textile substrates. Leuco colorants are compounds that are substantially colorless or only slightly colored but are capable of developing a strong color upon activation. One advantage of using leuco compounds in laundry care compositions is that such compounds, which are colorless until activated, enable the laundry care composition to take on its own color. Leuco colorants generally do not alter the primary color of the laundry care composition. Thus, manufacturers of such compositions can formulate colors that are most attractive to consumers without worrying that added ingredients (eg, bluing agents) will affect the final color value of the composition.

The range of textiles found in consumer households is very large and often includes garments constructed from various natural and synthetic fibres, and of these fibres in the same wash load or even in the same garment mixture. These textiles can be constructed in various ways and can include any of a number of finishes available to manufacturers. The amount of any such finishes retained on consumer textiles depends on a number of factors, including the durability of the finish under the specific washing conditions employed by the consumer, the specific detergents and additives the consumer may have used, and the textiles The number of cycles that have been washed. Depending on the history of each textile, finishes may be present to varying degrees or substantially absent, while other materials present in the wash or rinse cycle and contaminants encountered during wear may begin to accumulate on the textile.

Those skilled in the art are keenly aware that any detergent formulation used by a consumer will encounter textiles representing all possible, and that it is not only possible but practical to expect the formulation to behave in a manner on some textiles compared to others. There will be significant differences. These differences can be found through routine experimentation. For example, the leuco colorants of the present invention have been found to increase the whiteness of consumer aged garments and garments to which fabric enhancers have been applied to a greater extent than the leuco colorants have been removed by continuous laundering Finishing agent for the whiteness of new clothes. Therefore, formulations containing such leuco colorants may be preferred over traditional formulations, and even formulations containing conventional shade modifiers, since newer garments generally have less yellowing problems, while older consumers' Ageing clothes are more prone to yellowing problems. The leuco colorants of the present invention have a preference for increasing the whiteness of aged garments relative to clean new garments, which is greater than that exhibited by many conventional hue modifiers.

As described above, in a first embodiment, the present invention provides a leuco composition comprising at least one leuco compound comprising a leuco moiety and a leuco moiety covalently bound to the leuco moiety An alkylene oxide moiety, wherein the alkylene oxide moiety comprises at least one ethylene oxide group and at least one propylene oxide group.

The leuco compound may comprise any suitable leuco moiety as defined above. In one aspect, the leuco moiety is preferably selected from the group consisting of diarylmethane leuco moieties, triarylmethane leuco moieties, oxazine moieties, thiazine moieties, hydroquinone moieties and arylaminophenol moieties.

Diarylmethane leuco moieties suitable for use herein include, but are not limited to, monovalent or multivalent diarylmethylene moieties capable of forming the second colored state described herein. Suitable examples include, but are not limited to, moieties derived from Michler's methane, diarylmethylene groups substituted with -OH groups (eg, Michler alcohols) and ethers and esters thereof, groups cleavable by photo Groups such as -CN group substituted diarylmethylene (bis(p-N,N-dimethyl)phenyl)acetonitrile), and similar such moieties.

In a more particularly preferred aspect, the leuco moiety is derived by removing one or more hydrogen atoms from the structures of formula (I), (II), (III), (IV) or (V) below unit price or multi price part

wherein the ratio of formulae I to V to their oxidized forms is at least 1:19, 1:9 or 1:3, preferably at least 1:1, more preferably at least 3:1, most preferably at least 9:1 or even 19:1 1.

In the structure of formula (I), wherein each individual _R0 , _Rm and _Rp group on each of rings A, B and C is independently selected from hydrogen, deuterium and R5 ^; each R ⁵ is independently selected from halogen, nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl,—(CH ₂ ) _n —O—R ¹ ,— (CH ₂ ) _n ─NR ¹ R ² , ─C(O)R ¹ , ─C(O)OR ¹ , ─C(O)O ^- , ─C(O)NR ¹ R ² , ─OC(O) R ¹ , ─OC(O)OR ¹ , ─OC(O)NR ¹ R ² , ─S(O) ₂ R ¹ , ─S(O) ₂ OR ¹ , ─S(O) ₂ O ^- , ─S (O) ₂ NR ¹ R ² , ─NR ¹ C(O)R ² , ─NR ¹ C(O)OR ² , ─NR ¹ C(O)SR ² , ─NR ¹ C(O)NR ² R ³ , ─P(O) ₂ R ¹ , ─P(O)(OR ¹ ) ₂ , ─P(O)(OR ¹ )O ^- and ─P(O)(O ^- ) ₂ ; where subscript n is from 0 to 4, preferably an integer from 0 to 1, most preferably 0; wherein two R _o on different A, B and C rings can combine to form a five-membered or more fused ring; when When the fused ring is a six- or more-membered ring, two R _o on different A, B, and C rings can combine to form an organic linker that optionally contains one or more heteroatoms; in one embodiment, Two R _o on different A, B and C rings combine to form a heteroatom bridge selected from -O- and -S-, thereby forming a six-membered fused ring; R _o and R _m on the same ring or on the same ring The R _m and R _p may combine to form an aliphatic fused ring or an aromatic fused ring, any of which may contain a heteroatom; on at least one of the three rings A, B or C, R _o and Preferably at least two, more preferably at least three, most preferably all four of the _Rm groups are hydrogen, preferably all four _R0 on at least two of rings A, B and C. and _Rm groups are hydrogen; in some embodiments, all _R0 and _Rm groups on rings A, B, and C are hydrogen; preferably each _Rp is independently selected from hydrogen, ^─OR1 , and -NR ¹ R ² ; no more than two, preferably no more than one R _p is hydrogen, preferably all R _p are not hydrogen; more preferably at least one, preferably two, most preferably all three R _p are - NR ¹ R ² ; in some embodiments, one or even both of rings A, B, and C may be independently selected C ₃ -C ₉ containing one or two heteroatoms independently selected from O, S, and N Replacement of heteroaryl rings optionally substituted with _one or more independently selected R ⁵ groups; G independently selected from hydrogen, deuterium, C ₁ -C _{16 alkoxides} , phenate , bisphenoxide, nitrite, nitrile, alkylamine, imidazole, arylamine, polyoxyalkylene, halide, alkylsulfide, arylsulfide, or phosphine oxide; in one aspect, G The fraction of [(deuterium)/(deuterium+hydrogen)] is at least 0.20, preferably at least 0.40, even more preferably at least 0.50, and most preferably at least 0.60 or even at least 0.80; wherein R ¹ , Any two of R ² and R ³ can be combined to form a five-membered ring or more, the ring optionally containing one or more other members selected from the group consisting of—O—,—NR ^15— and—S— of heteroatoms.

In the structures of formulae (II)-(III), e and f are independently integers from 0 to 4; each R ²⁰ and R ²¹ are independently selected from halogen, nitro, alkyl, substituted alkyl,- NC(O)OR ¹ , ─NC(O)SR ¹ , ─OR ¹ and ─NR ¹ R ² ; each R ²⁵ is independently selected from monosaccharide moieties, disaccharide moieties, oligosaccharide moieties and polysaccharide moieties, ─C (O)R ¹ , —C(O)OR ¹ , —C(O)NR ¹ R ² ; and each of R ²² and R ²³ is independently selected from hydrogen, alkyl, and substituted alkyl.

In the structure of formula (IV), R ³⁰ is located in the ortho or para position of the bridged amine moiety and is selected from -OR ³⁸ and -NR ³⁶ R ³⁷ , each R ³⁶ and R ³⁷ are independently selected from hydrogen, alkyl , substituted alkyl, aryl, substituted aryl, acyl, R ⁴ , ─C(O)OR ¹ , ─C(O)R ¹ and ─C(O)NR ¹ R ² ; R ³⁸ is selected from hydrogen , acyl, ─C(O)OR ¹ , ─C(O)R ¹ , and ─C(O)NR ¹ R ² ; g and h are independently integers from 0 to 4; each R ³¹ and R ³² are independently Selected from alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, ─(CH ₂ ) _n ─O─R ¹ , ─(CH ₂ ) _n ─NR ¹ R ² , ─C(O)R ¹ , ─C(O)OR ¹ , ─C(O)O ^- , ─C(O)NR ¹ R ² , ─OC(O)R ¹ , ─OC(O)OR ¹ , ─OC(O)NR ¹ R ² , ─S(O) ₂ R ¹ , ─S(O) ₂ OR ¹ , ─S(O) ₂ O ^- , ─S(O) ₂ NR ¹ R ² , ─NR ¹ C(O)R ² , ─NR ¹ C(O)OR ² , ─NR ¹ C(O)SR ² , ─NR ¹ C(O)NR ² R ³ , ─P(O) ₂ R ¹ , ─P(O)(OR ¹ ) ₂ , ─P(O)(OR ¹ )O ^- and ─P(O)(O ^- ) ₂ ; where subscript n is 0 to 4, preferably 0 to 1 Integer, most preferably 0;—NR ³⁴ R ³⁵ is in the ortho or para position of the bridged amine moiety, and R ³⁴ and R ³⁵ are independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl group, alkaryl, substituted alkaryl and R ⁴ ; R ³³ is independently selected from hydrogen, ─S(O) ₂ R ¹ , ─C(O)N(H)R ¹ , ─C(O)OR ¹ and ─C(O)R ¹ ; when g is 2 to 4, any two adjacent R ³¹ groups may combine to form a five-membered or more fused ring, wherein no more than two of the fused rings The atoms can be nitrogen atoms.

In the structure of formula (V), X ⁴⁰ is selected from oxygen atom, sulfur atom and NR ⁴⁵ ; R ⁴⁵ is independently selected from hydrogen, deuterium, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl group, substituted alkaryl, ─S(O) ₂ OH, ─S(O) ₂ O ^- , ─C(O)OR ¹ , ─C(O)R ¹ and ─C(O)NR ¹ R ² ; R ⁴⁰ and R ⁴¹ are independently selected from—(CH ₂ ) _n —O—R ¹ ,—(CH ₂ ) _n —NR ¹ R ² , wherein subscript n is an integer from 0 to 4, preferably 0 to 1 , most preferably 0; j and k are independently integers from 0 to 3; R ⁴² and R ⁴³ are independently selected from alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted Alkaryl, ─S(O) ₂ R ¹ , ─C(O)NR ¹ R ² , ─NC(O)OR ¹ , ─NC(O)SR ¹ , ─C(O)OR ¹ , ─C( O)R ¹ , ─(CH ₂ ) _n ─O─R ¹ , ─(CH ₂ ) _n ─NR ¹ R ² , where subscript n is an integer from 0 to 4, preferably 0 to 1, most preferably 0; R ⁴⁴ is -C(O)R ¹ , -C(O)NR ¹ R ² and -C(O)OR ¹ .

In the structures of formulae (I)-(V), any charge present in any of the foregoing groups is in equilibrium with an appropriate independently selected internal or external counterion. Appropriate independently selected external counterions may be cationic or anionic. Examples of suitable cations include, but are not limited to, one or more metals, preferably one or more metals selected from Group I and Group II, with Na, K, Mg and Ca being most preferred among these metals ; or organic cations such as iminium, ammonium and phosphonium. Examples of suitable anions include, but are not limited to: fluoride, chloride, bromide, iodide, perchlorate, bisulfate, sulfate, sulfamate, nitrate, dihydrogen phosphate, hydrogen phosphate, phosphoric acid Salt, bicarbonate, carbonate, methosulfate, ethosulfate, cyanate, thiocyanate, tetrachlorozincate, borate, tetrafluoroborate , acetate, chloroacetate, cyanoacetate, glycolate, glycine, methylaminoacetate, dichloro and trichloroacetate, 2-chloropropionate, 2 -Hydroxypropionate, glycolate, thioglycolate, thioacetate, phenoxyacetate, trimethylacetate, valerate, palmitate, acrylic acid Salt, oxalate, malonate, crotonate, succinate, citrate, methylene-bis-thioglycolate, ethylene-bis-iminoacetate, nitrilotriethyl acid salt, fumarate, maleate, benzoate, methylbenzoate, chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate , phthalates, terephthalates, indolyl acetates, chlorobenzene sulfonates, benzene sulfonates, toluene sulfonates, biphenyl sulfonates, and chlorotoluene sulfonates . Different counterions that can be used in place of those listed above are well known to those of ordinary skill in the art.

As mentioned above, the leuco compound contains an alkylene oxide moiety in addition to the leuco moiety. In one aspect, the alkylene oxide moiety comprises at least one ethylene oxide group and at least one propylene oxide group. In another aspect, the alkylene oxide moiety comprises 1 to about 20 ethylene oxide groups and 1 to about 20 propylene oxide groups. In the alkylene oxide moiety, the different alkylene oxide groups can be arranged in a block configuration or a random configuration. In one aspect, the alkyleneoxy groups of the alkyleneoxy moiety are arranged in a block configuration.

The alkylene oxide moiety can be covalently attached to the leuco moiety through any suitable linking group. In one aspect, the alkylene oxide moiety is covalently bound to the leuco moiety through a linking group selected from oxygen and nitrogen atoms. When the linking group is an oxygen atom, one valence of the oxygen atom is occupied by the alkylene oxygen moiety, and the second valence of the oxygen atom is occupied by the remainder of the leuco moiety. When the linking group is a nitrogen atom, one valence of the nitrogen atom is occupied by the remainder of the leuco moiety, and one valence of the nitrogen atom is occupied by the alkylene oxide moiety. The remaining valencies of the nitrogen atom can be occupied by any suitable group such as the second alkylene oxide moiety. In one aspect, the alkylene oxide moiety is covalently bound to the leuco moiety, preferably through a nitrogen atom. In this embodiment, the nitrogen atom and the alkylene oxide moiety together have the structure _— NR1 _{( C2H4O} ) ⁿ ( _C3H6O )qH, where _n and _q are independently selected from 1 to an integer of ⁵ , and R1 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and alkylene oxide moieties. In another aspect, the leuco compound comprises two alkylene oxide moieties, each alkylene oxide moiety covalently bonded to the leuco moiety through a nitrogen atom, wherein the nitrogen atom and the alkylene oxide moiety together have the structure

wherein n, q, r, and s are independently selected from integers from 0 to 5, the sum of n and r is 2 to 10, and the sum of q and s is 2 to 10. In a more particular aspect, the sum of n and r is 2 to 5, and the sum of q and s is 2 to 5.

The leuco compound included in the composition may comprise any suitable structure having the above-mentioned characteristics. In one aspect, the leuco compound conforms to the structure of formula (CI), (CII), (CIII), (CIV) or (CV) below

wherein the ratio of formulae CI to CV to its oxidized form is at least 1:19, 1:9 or 1:3, preferably at least 1:1, more preferably at least 3:1, most preferably at least 9:1 or even 19:1 1.

In the structure of formula (CI), each individual _R0 , _Rm and _Rp group on each of rings A, B and C is independently selected from hydrogen, deuterium and R5 ^; each R ⁵ is independently selected from halogen, nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, ─(CH ₂ ) _n ─O─R ¹ , ─( CH ₂ ) _n ─NR ¹ R ² , ─C(O)R ¹ , ─C(O)OR ¹ , ─C(O)O ^- , ─C(O)NR ¹ R ² , ─OC(O)R ¹ , ─OC(O)OR ¹ , ─OC(O)NR ¹ R ² , ─S(O) ₂ R ¹ , ─S(O) ₂ OR ¹ , ─S(O) ₂ O ^- , ─S( O) ₂ NR ¹ R ² , ─NR ¹ C(O)R ² , ─NR ¹ C(O)OR ² , ─NR ¹ C(O)SR ² , ─NR ¹ C(O)NR ² R ³ , ─P(O) ₂ R ¹ , ─P(O)(OR ¹ ) ₂ , ─P(O)(OR ¹ )O ^- and ─P(O)(O ^- ) ₂ ; where subscript n is from 0 to 4, preferably an integer from 0 to 1, most preferably 0; wherein two R _o on different A, B and C rings can combine to form a five-membered or more fused ring; when the fused ring When a six- or more-membered ring, two R _o on different A, B, and C rings can combine to form an organic linker optionally containing one or more heteroatoms; in one embodiment, different A , two R _o on the B and C rings combine to form a heteroatom bridge selected from -O- and -S-, thereby forming a six-membered fused ring; R _o and R _m on the same ring or R on the same ring _m and R _p may combine to form aliphatic fused rings or aromatic fused rings, any of which may contain heteroatoms; on at least one of the three rings A, B or C, R _o and R _m Preferably at least two, more preferably at least three, most preferably all four of the groups are hydrogen, preferably all four _R and R on at least two of _rings A, B and C group is hydrogen; in some embodiments, all R and R groups ^on rings ^A , B, and C are hydrogen; preferably each R _is independently selected from hydrogen, _-OR1 and _-NR1R ² ; no more than two, preferably no more than one R _p is hydrogen, preferably all R _p is not hydrogen; more preferably at least one, preferably two, most preferably all three R _p is -NR ¹ R ² ; in In some embodiments, one or even both rings of Rings A, B, and C may be independently selected C3 _{- C9} heteroaryl groups containing one or two heteroatoms independently selected from O, S, and N Ring substitution, the C3 _{- C9} heteroaryl ring is optionally substituted with one or more independently selected R5 groups ^; G is independently selected from hydrogen, deuterium, _C1 - _C16 alkoxides, phenates ,pair phenate, nitrite, nitrile, alkylamine, imidazole, arylamine, polyoxyalkylene, halide, alkylsulfide, arylsulfide, or phosphine oxide; in one aspect, the fraction of G [(deuterium )/(deuterium+hydrogen)] is at least 0.20, preferably at least 0.40, even more preferably at least 0.50, and most preferably at least 0.60 or even at least 0.80; wherein R ¹ , R ² and R ³ are attached to the same heteroatom Any two of these may be combined to form a five-membered or more membered ring, optionally containing one or more additional heteroatoms selected from —O—, ^—NR15— , and —S—.

In the structures of formulae (CII) and (CIII), the variables e and f are independently integers from 0 to 4; each R ²⁰ and R ²¹ are independently selected from halogen, nitro, alkyl, substituted alkyl, ─NC(O)OR ¹ , ─NC(O)SR ¹ , ─OR ¹ and ─NR ¹ R ² ; each R ²⁵ is independently selected from a monosaccharide moiety, a disaccharide moiety, an oligosaccharide moiety and a polysaccharide moiety, ─ C(O)R ¹ , —C(O)OR ¹ , —C(O)NR ¹ R ² ; and each of R ²² and R ²³ is independently selected from hydrogen, alkyl, and substituted alkyl.

In the structure of formula (CIV), R ³⁰ is located in the ortho or para position of the bridged amine moiety and is selected from -OR ³⁸ and -NR ³⁶ R ³⁷ , each R ³⁶ and R ³⁷ independently selected from hydrogen, alkyl , substituted alkyl, aryl, substituted aryl, acyl, R ⁴ , ─C(O)OR ¹ , ─C(O)R ¹ and ─C(O)NR ¹ R ² ; R ³⁸ is selected from hydrogen , acyl, ─C(O)OR ¹ , ─C(O)R ¹ , and ─C(O)NR ¹ R ² ; g and h are independently integers from 0 to 4; each R ³¹ and R ³² are independently Selected from alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, ─(CH ₂ ) _n ─O─R ¹ , ─(CH ₂ ) _n ─NR ¹ R ² , ─C(O)R ¹ , ─C(O)OR ¹ , ─C(O)O ^- , ─C(O)NR ¹ R ² , ─OC(O)R ¹ , ─OC(O)OR ¹ , ─OC(O)NR ¹ R ² , ─S(O) ₂ R ¹ , ─S(O) ₂ OR ¹ , ─S(O) ₂ O ^- , ─S(O) ₂ NR ¹ R ² , ─NR ¹ C(O)R ² , ─NR ¹ C(O)OR ² , ─NR ¹ C(O)SR ² , ─NR ¹ C(O)NR ² R ³ , ─P(O) ₂ R ¹ , ─P(O)(OR ¹ ) ₂ , ─P(O)(OR ¹ )O ^- and ─P(O)(O ^- ) ₂ ; where subscript n is 0 to 4, preferably 0 to 1 Integer, most preferably 0;—NR ³⁴ R ³⁵ is in the ortho or para position of the bridged amine moiety, and R ³⁴ and R ³⁵ are independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl group, alkaryl, substituted alkaryl and R ⁴ ; R ³³ is independently selected from hydrogen, ─S(O) ₂ R ¹ , ─C(O)N(H)R ¹ , ─C(O)OR ¹ and ─C(O)R ¹ ; when g is 2 to 4, any two adjacent R ³¹ groups may combine to form a five-membered or more fused ring, wherein no more than two of the fused rings The atoms can be nitrogen atoms.

In the structure of formula (CV), X ⁴⁰ is selected from oxygen atom, sulfur atom and NR ⁴⁵ ; R ⁴⁵ is independently selected from hydrogen, deuterium, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl , substituted alkaryl, ─S(O) ₂ OH, ─S(O) ₂ O ^- , ─C(O)OR ¹ , ─C(O)R ¹ and ─C(O)NR ¹ R ² ; R ⁴⁰ and R ⁴¹ are independently selected from ─(CH ₂ ) _n ─O─R ¹ , ─(CH ₂ ) _n ─NR ¹ R ² , wherein subscript n is an integer from 0 to 4, preferably 0 to 1, Most preferably 0; j and k are independently integers from 0 to 3; ^R42 and ^R43 are independently selected from alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkane Aryl, ─S(O) ₂ R ¹ , ─C(O)NR ¹ R ² , ─NC(O)OR ¹ , ─NC(O)SR ¹ , ─C(O)OR ¹ , ─C(O ) R ¹ , ─(CH ₂ ) _n ─O─R ¹ , ─(CH ₂ ) _n ─NR ¹ R ² , where subscript n is an integer from 0 to 4, preferably 0 to 1, most preferably 0 ; R ⁴⁴ is -C(O)R ¹ , -C(O)NR ¹ R ² and -C(O)OR ¹ .

In the structures of formulae (I) to (V) and (CI) to (CV), R ¹ , R ² , R ³ and R ¹⁵ are independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl and R ⁴ ; wherein R ⁴ is an organic group consisting of one or more organic monomers, wherein the monomer molecular weight is 28-500, preferably 43- 350, even more preferably in the range of 43-250, wherein the organic group may be moiety substituted with one or more additional leuco colorant moieties conforming to the structures of formulae I to V. ^In one aspect, R is selected from the group consisting of alkylene oxides (polyethers), oxoalkylene oxides (polyesters), oxoalkylene amines (polyamides), epichlorohydrin, quaternized epoxy Chloropropanes, alkyleneamines, hydroxyalkylenes, acyloxyalkylenes, carboxyalkylenes, alkoxycarbonylalkylenes and sugars. Where any leuco colorant contains R4 groups with ^three or more adjacent monomers, that leuco colorant is defined herein as a "polymeric leuco colorant". Those skilled in the art know that the properties of a compound with respect to any of a number of characteristic properties (eg, solubility, partition, deposition, removal, staining, etc.) related to the number. Thus, one skilled in the art can adjust the arrangement, identity and number of the adjoining cells to change any particular property in a more or less predictable manner.

In the structures of formulae (CI) to (CV), R ¹ , R ² and R ³ are independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl base and R ⁴ . R4 is an alkylene oxide moiety as described above ^.

Furthermore, in the structures of formulae (CI) to (CV), any charge present in any of the foregoing groups is in equilibrium with an appropriate independently selected internal or external counterion. Appropriate independently selected external counterions may be cationic or anionic. Examples of suitable cations include, but are not limited to: one or more metals, preferably selected from Group I and Group II metals, with Na, K, Mg and Ca being most preferred among these metals; or organic cations, Examples are imide ions, ammonium ions and phosphoniums. Examples of suitable anions include, but are not limited to: fluoride, chloride, bromide, iodide, perchlorate, bisulfate, sulfate, sulfamate, nitrate, dihydrogen phosphate, hydrogen phosphate, phosphoric acid Salt, Bicarbonate, Carbonate, Methylsulfate, Ethosulfate, Cyanate, Thiocyanate, Tetrachlorozincate, Borate, Tetrafluoroborate, Acetate, Chlorine Acetate, cyanoacetate, glycolate, glycine, methylaminoacetate, dichloro and trichloroacetate, 2-chloropropionate, 2-hydroxypropionate, Glycolate, Thioglycolate, Thioacetate, Phenoxyacetate, Trimethylacetate, Valerate, Palmitate, Acrylate, Oxalate, Malonate, Croton acid salt, succinate, citrate, methylene-bis-thioglycolate, ethylene-bis-iminoacetate, nitrilotriacetate, fumarate, maleate , benzoate, methylbenzoate, chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate, phthalate, terephthalate acid salts, indolyl acetates, chlorobenzene sulfonates, benzene sulfonates, toluene sulfonates, biphenyl sulfonates and chlorotoluene sulfonates. Different counterions that can be used in place of those listed above are well known to those of ordinary skill in the art.

Thus, in one aspect, the leuco compound is a triarylmethane leuco compound of formula (CI)

wherein the ratio of formula (CI) to its oxidized form is at least 1:3; wherein each individual _R0 , _Rm and _Rp group on each of rings A, B and C is independently selected from hydrogen, Deuterium and R ⁵ ; wherein each R ⁵ is independently selected from halogen, nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, —(CH ₂ ) _n ─O─R ¹ , ─(CH ₂ ) _n ─NR ¹ R ² , ─C(O)R ¹ , ─C(O)OR ¹ , ─C(O)O ^- , ─C(O)NR ¹ R ² , ─OC(O)R ¹ , ─OC(O)OR ¹ , ─OC(O)NR ¹ R ² , ─S(O) ₂ R ¹ , ─S(O) ₂ OR ¹ , ─S( O) ₂ O ^- , ─S(O) ₂ NR ¹ R ² , ─NR ¹ C(O)R ² , ─NR ¹ C(O)OR ² , ─NR ¹ C(O)SR ² , ─NR ¹ C(O)NR ² R ³ , ─P(O) ₂ R ¹ , ─P(O)(OR ¹ ) ₂ , ─P(O)(OR ¹ )O ^- and ─P(O)(O ^- ) ₂ ; wherein subscript n is an integer from 0 to 4, preferably 0 to 1, most preferably 0; wherein R _o and R _m groups on at least one of the three rings A, B or C At least one group is hydrogen; each R _p is independently selected from hydrogen, ─OR ¹ and ─NR ¹ R ² ; wherein G is independently selected from hydrogen, deuterium, C ₁ -C ₁₆ alkoxides, phenates, bisphenols Salts, nitrites, nitriles, alkylamines, imidazoles, arylamines, polyalkylene oxides, halides, alkyl sulfides, aryl sulfides and phosphine oxides; wherein R ¹ , R ² and R ³ are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and R4 ^; R4 is an alkylene oxide moiety ^; and any of which is present in the compound The charge is balanced with an appropriate independently selected internal or external counterion.

In one aspect, preferred leuco compounds include those conforming to the structure of formula (CVI),

wherein each R4 is independently selected from H, methyl, ethyl, (( _{CH2CH2O ) a (} ^C3H6O ) _b )H and mixtures thereof _; preferably at least one R4 group is ⁽ ( _{CH2CH2O ) a} ( _C3H6O ) _b )H _; wherein each subscript a is independently an integer from 1-100, each subscript b is independently an integer from 0-50, and where all ^The sum of all independently selected integers of a in R4 groups does not exceed 100, and the sum of all independently selected integers of b in all ^R4 groups does not exceed 50. Preferably at least two R4 groups are selected from methyl and ethyl, most preferably at least one N in structure (CVI ⁾ is substituted with two ^R4 groups selected from methyl and ethyl, preferably methyl .

In another aspect, highly preferred leuco compounds include those conforming to the structure of formula (CVII),

wherein each subscript c is independently 0, 1 or 2, preferably each c is 0 or ¹ , more preferably the two independently selected values of c are the same; each R is independently selected from H, Me , Et, (( _CH2CH2O ) _a ( _C3H6O ) _b )H and mixtures thereof _; preferably, each R4 is ⁽ ( _{CH2CH2O ) a ( C3H6O ) b} ) H, wherein each subscript a is independently an integer of 1-50, more preferably 1-25, even more preferably 1-20, 1-15, 1-10, 1-5 or even 1-2 ; each subscript b is independently an integer of 0-25, more preferably 0-15, even more preferably 1-5 or even 1-3, and wherein all independently selected integers of a in the leuco colorant The sum of not more than 100, more preferably not more than 80, most preferably not more than 60, 40, 20, 10 or even not more than 5, and the sum of all independently selected b integers in the leuco colorant does not exceed 50 , more preferably no more than 40, most preferably no more than 30, 20 or even 10. In particularly preferred aspects, each subscript _c is ¹ , each R4 is (( _{CH2CH2O ) a} ( _C3H6O ) _b )H, and each subscript a is 1-5 Integers, each subscript b is an integer from 1 to 5, the sum of all independently selected integers of a in the leuco compound is 4 to 10, and the sum of all independently selected integers of b in the leuco colorant is 5 to 15.

In another aspect, highly preferred leuco compounds include those conforming to the structure of formula (CVIII),

wherein ^R8 is H or _CH3 , and each subscript b independently averages about 1 to 2.

In one aspect, the leuco colorant of the present invention has a surface tension value greater than 45 mN/m, more preferably greater than 47.5 mN/m, most preferably greater than 50 mN/m. In another aspect, the surface tension value of the second colored state of the leuco colorant is greater than 45 mN/m, more preferably greater than 47.5 mN/m, and most preferably greater than 50 mN/m. In yet another aspect of the invention, the surface tension value of both the leuco colorant and its corresponding second colored state is greater than 45 mN/m, more preferably greater than 47.5 mN/m, most preferably greater than 50 mN/m.

The leucotriarylmethane compounds described herein can be produced by any suitable synthetic method. For example, such compounds can be reacted by an acid-catalyzed condensation reaction between an aromatic aldehyde and an electron-rich aryl coupling agent (eg, in an amount of about 2 molar equivalents of aryl coupling agent to 1 molar equivalent of aromatic aldehyde) ) to prepare. The aromatic aldehyde can be any suitable compound comprising an aromatic moiety (eg, an aryl moiety, a substituted aryl moiety, a heteroaromatic moiety, or a substituted heteroaromatic moiety) having an aldehyde group covalently attached thereto. . In one aspect, the aromatic aldehyde is preferably ^a substituted benzaldehyde, which preferably contains ^a group having the structure -OR1 or ^-NR1R2 in the para position relative to the aldehyde group. In another aspect, the aromatic aldehyde is preferably a substituted benzaldehyde comprising the group -NR ¹ R ² in the para position relative to the aldehyde group, wherein R ¹ and R ² are selected from hydrogen, methyl or ethyl (more preferably methyl).

As mentioned above, the condensation reaction uses an aryl coupling agent in addition to the aromatic aldehyde. To produce leucotriarylmethane compounds, the condensation reaction typically utilizes at least two molar equivalents of an aryl coupling agent per molar equivalent of aromatic aldehyde. In one aspect, two molar equivalents of the aryl coupling agent used in the reaction can be provided using a single aryl coupling agent compound. In another aspect, the reaction can be carried out using a mixture of two molar equivalents of two or more different aryl coupling agents. In this embodiment, two or more different aryl coupling agents can be used in any combination or relative ratio, so long as the mixture totals at least about two molar equivalents of aryl coupling for every molar equivalent of aromatic aldehyde agent can be. In such embodiments, the two or more different aryl coupling agents may differ, eg, in the number and/or nature of substituents attached to the aryl moiety. In one aspect, the reaction can utilize a first aryl coupling agent and a second aryl coupling agent, wherein the first aryl coupling agent comprises a first oxyalkylene group having a distribution of first oxyalkylene groups or a polyoxyalkylene moiety, and the second aryl coupling agent comprises a second oxyalkylene group or polyoxyalkylene moiety having a different distribution of second oxyalkylene groups than the first distribution. For example, in one aspect, the first aryl coupling agent may comprise an oxyalkylene moiety composed of ethylene oxide groups, such as AC-I below, and the second aryl coupling agent may comprise an oxyethylene moiety composed of ethylene oxide groups Polyoxyalkylene moieties composed of alkyl groups and propylene oxide groups, such as AC-II below.

wherein the subscripts a, b, c and d are independently selected from integers from 0 to 5; the sum of a and b of the coupling agents selected from AC-I and AC-II is 2 to 10, and c in AC-II The sum of and d is 2 to 10. In a more particular aspect, the sum of a and b of the coupling agent selected from AC-I and AC-II is 2 to 5, and the sum of c and d in AC-II is 2 to 5. In one embodiment, the sum of subscripts a and b in AC-I is 2 or 3; and the sum of subscripts a and b in AC-II is 2 or 3, and the sum of subscripts c and d in AC-II The sum is 1 to 5, preferably 2 to 4, or even 2 to 3. Coupling agents AC-I and AC-II can be combined in any ratio as long as the amount of coupling agent used is sufficient to provide at least two molar equivalents relative to the equivalents of aromatic aldehyde used in the acid-catalyzed condensation reaction to produce the leuco compound. Can.

In one aspect, for example, one equivalent of p-N,N-dimethylbenzaldehyde is condensed with at least two molar equivalents of the mixture of aryl coupling agents AC-I and AC-II shown above, wherein for aryl base coupling agent AC-I, the sum of subscripts a and b is 2 or 3, preferably 2, and wherein preferably a and b are each 1; wherein for aryl coupling agent AC-II, subscript a The sum of and b is 2 or 3, preferably 2, and wherein preferably a and b are each 1, and the sum of the subscripts c and d is on average about 2.5 to 3.0, and wherein at least one of c or d is 1.

One of ordinary skill in the art will recognize that when two or more different aryl coupling agents are used in the preparation of the leuco compounds herein, the expected product from the reaction will contain non-different (non- distinct) coupling agents (for as many different coupling agents as possible) and cross-coupled leuco compounds containing a mixture of the aryl coupling agents used. For example, when prepared using the two different aryl coupling agents A and B used in approximately equimolar amounts, the product distribution (excluding any perturbations due to differences in reactivity) would include about 25% of the two A-couples The leuco compound of the coupling agent, 25% of the leuco compound containing two B coupling agents, and 50% of the leuco compound containing one A coupling agent and one B coupling agent.

Exemplary leuco compositions can be prepared according to the general methods described below for compositions in which the aryl aldehyde conforms to Ar-C(O)H but is readily adaptable.

The four-necked flask was equipped with an overhead stirrer, condenser, temperature controller, heating mantle and nitrogen inlet. Then, about 2 moles of the aryl coupling agent or mixture of aryl coupling agents was added to the flask and heated to about 65-71°C. During heating, about 1 mole of Ar-C(O)H and a catalytic amount (about 0.4 moles) of urea pre-dissolved in a small amount of water were added. After the above chemicals were mixed, about 1.2 moles of hydrochloric acid (in the form of Muriatic acid) were added dropwise to control the temperature below 90-100°C. After the addition of hydrochloric acid, the reaction was stirred at 95-100°C for about 7 hours.

A variety of methods can be used to recover the leuco colorants synthesized by the above methods. One method is to neutralize the reaction product to a pH of about 9 and remove the water by rotary evaporation under reduced pressure. The resulting viscous mass is diluted with an organic solvent such as isopropanol and filtered to remove inorganic salts. Evaporation of the organic solvent gave the final product.

In another embodiment, the present invention provides a leuco composition obtained by (i) providing one molar equivalent of an aromatic aldehyde, (ii) providing about two molar equivalents of an aryl coupling agent or aryl group Mixtures of coupling agents, wherein at least one aryl coupling agent comprises a covalently bound oxyalkylene or polyoxyalkylene moiety, wherein the oxyalkylene or polyoxyalkylene moiety comprises at least one ethylene oxide group and at least one propylene oxide groups, (iii) combining the aromatic aldehyde and one or more aryl coupling agents in a suitable reaction vessel, (iv) adding 0.01 to 0.5 equivalents of urea, (v) adding industrial grade hydrochloric acid to achieve a pH between about 0 and 3, (vi) heating the mixture between 60°C and 120°C for 2 hours to 12 hours, (vii) adjusting the pH to at least about 7, and (viii) ) at least a portion of the salt formed during neutralization is separated from the liquid product; wherein the leuco composition comprises at least one leuco compound comprising a leuco moiety and covalently bound to the leuco The alkylene oxide moiety of the color moiety, wherein the alkylene oxide moiety comprises at least one ethylene oxide group and at least one propylene oxide group. In one such embodiment, the leuco compound has the structure of formula (CVII) above, wherein the value of at least one independently selected subscript b is at least one.

The amount of leuco colorant used in the laundry care compositions of the present invention can be any level suitable to achieve an increase in Whiteness Index (WI CIE) of white fabrics or textiles. In one aspect, the laundry care composition comprises about 0.0001 wt% to about 1.0 wt%, preferably 0.0005 wt% to about 0.5 wt%, even more preferably about 0.0008 wt% to about 0.2 wt%, most preferably 0.004 wt% The leuco colorant is present in an amount ranging from % to about 0.1% by weight.

In another aspect, the laundry care composition comprises 0.0025 to 5.0 meq/kg, preferably 0.005 to 2.5 meq/kg, even more preferably 0.01 to 1.0 meq/kg, most preferably 0.05 to 0.50 meq/kg /kg of leuco colorant, where the unit of milliequivalents/kg refers to milliequivalents of leuco fraction per kg of laundry composition. For leuco colorants containing more than one leuco moiety, the number of milliequivalents is related to the number of millimoles of leuco colorant by the following formula: (mmol of leuco colorant) x (number of milliequivalents of leuco moiety/ millimoles of leuco colorant) = milliequivalent of leuco moiety. Where there is only one leuco moiety per leuco colorant, the milliequivalents/kg will be equal to millimoles of leuco colorant/kg laundry care composition.

The leuco composition of the present invention may contain other compounds in addition to the one or more leuco compounds, one or more antioxidant compounds and one or more solvents described above. For example, the leuco composition may contain up to about 2% by weight of salts (eg, sodium chloride or sodium sulfate), unreacted starting materials used in the preparation of one or more leuco compounds, the Impurities from side reactions and leuco compounds or degradation products of such impurities. Specific non-limiting examples of such materials include compounds of formula (DI)-(DV)

In the structures of formulae (DI)-(DV), R ¹⁰¹ and R ¹⁰² are independently selected from hydrogen, alkyl (eg, methyl), and oxyalkylene. The oxyalkylene group may contain any suitable number of oxyalkylene repeating units (eg, ethylene oxide and/or propylene oxide), such as the ranges disclosed above for the leuco compounds present in the leuco composition. Such oxyalkylene groups of R ¹⁰¹ and R ¹⁰² can be independently selected from hydrogen, CH=CH ₂ , -CH ₂ -CH=CH ₂ , -CH=CH-CH ₃ , -CH ₂ -CHO, -CH ( _CH3 )-CHO, _-CH2 -CO- _CH3 , _-CH2 -COOH, -CH( _CH3 )-COOH, _-CH2 - _CH2Cl , -CHCl- _CH3 , _-CH2 -CH Members of ₂ -CH2Cl, _-CH2 -CHCl- _CH3 and -CHCl- _{CH2 - CH3} are capped. Furthermore, the groups R ¹⁰¹ and R ¹⁰² may combine to form a group having the structure ─CH ₂ CH ₂ ─O—CH ₂ CH ₂ ─, which together with a nitrogen atom forms a morpholine ring. Other compounds that may be present in the leuco composition include compounds of formula (DVI)–(DIX)

Each aryl moiety of the compounds of formula (DVI)–(DIX) may independently be unsubstituted, or typically substituted in the para position with a nitro group or a group having the structure ─NR ¹⁰¹ R ¹⁰² , wherein R ¹⁰¹ and R ¹⁰² are independently is selected from the above groups. Additional compounds that may be present in the leuco composition include phenols and aminophenols, usually in the para position relative to the hydroxyl group, containing a group having the structure ─NR ¹⁰¹ R ¹⁰² , wherein R ¹⁰¹ and R ¹⁰² are independently selected from the above groups . The leuco composition may also contain compounds of formula (DX) and (DXI)

In the structures of (DX) and (DXI), the aryl and cyclohexadienyl moieties may be unsubstituted, or typically substituted in the para position with a nitro group or a group having the structure ─NR ¹⁰¹ R ¹⁰² , where R ¹⁰¹ and R ¹⁰² are independently selected from the above groups. The leuco composition may also contain condensation products of certain compounds described above, such as compounds of formula (DXII)

As noted above, the leuco composition may also contain a colored (eg, oxidized) form of one or more leuco compounds present in the composition. In the case of a leucotriarylmethane colorant, the oxidized form of the leucotriarylmethane colorant (which contains a central carbocation) may be combined with anions such as those described above present in the leuco composition as suitable for use in one or Charge-balancing counterions of various leuco compounds form adducts.

The aforementioned unreacted starting materials and impurities may be present in the leuco composition in any suitable amount. Preferably, these materials and impurities are present in the leuco composition in relatively small amounts that do not adversely affect the performance of the leuco colorant(s) to any substantial extent. Excluding inorganic salts, unreacted starting materials and water, in preferred embodiments, the impurities are present at less than 10% by weight, preferably less than 5% by weight, and more preferably less than 2% by weight relative to the reactive leuco compound amount exists.

The leuco composition may contain any suitable amount of the leuco compound as described above. Furthermore, the leuco composition may contain any suitable solvent in addition to one or more leuco compounds. In one aspect, the leuco composition comprises selected from the group consisting of water, ethylene glycol, propylene glycol, glycerin, poly(ethylene glycol), poly(propylene glycol), copolymers of ethylene oxide and propylene oxide, and their solvent in the mixture. In another aspect, the leuco composition comprises the group consisting of poly(ethylene glycol), poly(propylene glycol), copolymers of ethylene oxide and propylene oxide, the nonionic surfactants disclosed below, and mixtures thereof in the solvent. In a preferred embodiment, the leuco composition is dissolved in a poly(ethylene glycol) such as PEG200 prior to its incorporation into the laundry care composition.

HP136和AOX-1)、生育酚山梨酸酯、丁基化羟基苯甲酸及其盐、没食子酸及其烷基酯、尿酸及其盐和烷基酯、山梨酸及其盐、二羟基富马酸及其盐、芳族胺(例如

5057)及其混合物。在抗氧化剂是可与隐色组合物混溶的液体的情况下，抗氧化剂可充当溶剂或助溶剂。In one aspect, the leuco composition comprises an antioxidant compound in addition to one or more leuco compounds and any suitable solvent that may be present. The presence of antioxidant compounds serves to stabilize the composition and reduce the amount of leuco compounds that are prematurely converted to the second color state. In the composition, any suitable antioxidant compound may be used. In one aspect, the antioxidant compound is selected from hindered phenols (eg BHT, irganox 1135, irganox 1076, irganox 1010, irganox 1330 and irganox 1035), aromatic amines and derivatives thereof (eg irganox 5057), alpha-, beta- , γ-, δ-tocopherol, tropoline, 2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butylhydroquinone, tert-butylhydroxyanisole, lignin sulfonic acid and its salts, 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox ^TM ), 1,2-benzisothiazoline-3- Ketone (Proxel GXL ^™ ), benzofuran or benzopyran derivatives (such as those sold by Milliken and Company, Spartanburg, USA)

HP136 and AOX-1), tocopheryl sorbate, butylated hydroxybenzoic acid and its salts, gallic acid and its alkyl esters, uric acid and its salts and alkyl esters, sorbic acid and its salts, dihydroxyfumar Acids and their salts, aromatic amines (such as

5057) and mixtures thereof. Where the antioxidant is a liquid that is miscible with the leuco composition, the antioxidant can act as a solvent or co-solvent.

The leuco composition of the present invention should be stored and transported in a closed container to prevent contamination by dust, moisture or other foreign matter. Preferably, the leuco composition is stored and shipped in an air-tight container. The shipping container may be constructed of a material with a low oxygen permeability coefficient P, where P=(permeation)(membrane thickness)/(surface area)(time)(pressure drop across the membrane) in [cm ^3. cm]/[ cm ^2. s. (cmHg)]. A suitable container may consist of a material wherein the P x 10 ¹⁰ is less than 10, more preferably less than 5, most preferably less than 2 at 30°C. This limits the exposure of the material to oxygen and limits the conversion of leuco compounds to a second colored state during storage and transport.

SM 6、

SM 13、

SM 15、

SM EX、

SM LP。任选地，HDPE容器可以含有用于保护内容物免受紫外线和可见光伤害的添加剂，例如

SM LP*手提袋等。另外，HDPE容器可能含有由EVOH阻渗透层或可由Schütz包装体系获得的Dualprotect体系提供的附加保护。The container may consist of bulk cargo in any suitable size tanker, tote, barrel, carboy or steel cylinder. Most preferred containers are made of stainless steel or HDPE. The container may be an open container or a sealed mouth container. The stainless steel container can be unlined or optionally lined with any suitable coating (eg epoxy or epoxy novolac coating). Some containers may contain at least one drain valve, and the containers are preferably sturdy, stackable and DOT/UN certified. Suitable packaging is available from various suppliers such as General Steel, Mauser, Schütz, Cardinal Packaging or others. For non-limiting examples, suitable containers may be Ecobulk MX, Ecobulk MX-EX, Ecobulk MX-EV, Ecobulk MX, Cleancert, Ecobulk MX-EX-EV Cleancert, EcobulkSX-EX and Ecobulk MX impeller by Schütz , provided by Mauser

SM 6.

SM 13.

SM 15,

SM EX,

SM LP. Optionally, the HDPE container may contain additives to protect the contents from UV and visible light, such as

SM LP* tote bags and more. Additionally, the HDPE container may contain additional protection provided by an EVOH barrier layer or the Dualprotect system available from Schütz packaging systems.

As explained above, the leuco compositions of the present invention are relatively stable and do not require specific shipping or packaging requirements. For example, the material does not need to be packaged under an inert atmosphere or shipped under climate control to remain stable. However, the storage stability of the leuco composition can be improved by implementing certain measures. For example, it may be preferable to transport and store this or other less stable materials in an oxygen-deficient atmosphere, cold temperatures, or both. One way to create an oxygen-deficient atmosphere is to use an inert gas such as nitrogen, argon, or carbon dioxide. The vessel can be purged with an inert gas for a period of time, or by evacuating the vessel and backfilling the vessel with an inert gas. When purging, the purging time should be at least three times longer, and more preferably five times longer, than the time required to fill the headspace in the vessel. During purging or backfilling, the internal pressure should be close to atmospheric pressure, or slightly above atmospheric pressure. The preferred internal pressure range is 0.5 to 2 atmospheres, more preferably 0.8 to 1.5 atmospheres, and most preferably 0.95 to 1.2 atmospheres. Those skilled in the art will recognize that the ideal pressure is the value under the conditions encountered during purging or backfilling, and when the temperature changes, the gas pressure will change, approximately obeying the ideal gas law. Alternatively, the material itself can be purged with an inert gas by bubbling the inert gas through the product for a period of time before or after packaging.

For any container in which the leuco composition of the present invention or even a less stable material is present, the percentage of container volume occupied by the material should be at least 50%, more preferably 80%, even more preferably 90% or even 95%, which in turn limits the volume that constitutes the headspace occupied by ambient air, inert gas, or mixtures thereof. For oxygen-sensitive materials, limiting the amount of oxygen present in the container will slow the conversion of the leuco compound to the second colored state. Furthermore, vessel designs that minimize the surface area of the interface between the material and the headspace are generally preferred. For this reason, transporting the material by means of restricting its movement within the container reduces the time-averaged surface area and may help improve the stability of the material, especially those containing slightly less stable leuco compounds .

As mentioned above, the materials of the present invention are stable enough to be stored and transported without climate control, where the temperature can range from -40°C to 60°C depending on the climate and location. However, lower temperatures are preferred. A suitable temperature range for storing and transporting chemicals is -30°C to 60°C, more preferably -10°C to 50°C, most preferably 0°C to 35°C.

Additional protection of the product, such as oxygen scavengers in films, sachets, or by direct incorporation into the packaging material, may be used to maintain an oxygen-deficient atmosphere within the container.

Any precautions for minimizing conversion of the leuco composition prior to incorporation into the laundry care compositions described above can be similarly applied to the storage and transportation of laundry care compositions comprising the leuco composition.

The leuco compounds and compositions described above are believed to be suitable for use in the treatment of textile materials, such as in domestic laundry methods. In particular, it is believed that due to the nature of the leuco compound, the leuco compound will deposit on the fibers of the textile material. Furthermore, once deposited on the textile material, the leuco compound can be converted into a coloured compound by applying an appropriate chemical or physical trigger that converts the leuco compound into its coloured form. For example, when a leuco compound is oxidized to an oxidized compound, the leuco compound can be converted to its colored form. By selecting an appropriate leuco moiety, the leuco compound can be designed to impart a desired hue to the textile material when the leuco compound is converted into its colored form. For example, leuco compounds that exhibit a blue tint when converted to their colored form can be used to counteract the yellowing of textile materials that typically occurs over time and/or repeated washing. Accordingly, in other embodiments, the present invention provides laundry care compositions comprising the leuco compounds described above, as well as domestic methods for treating textile materials (eg, methods for laundering laundry or garments).

Preferably, the leuco compound has a relative hue angle of 210 to 345, or even a relative hue angle of 240 to 320, or even a relative hue angle of 250 to 300 (eg, 250 to 290) when converted into its second color state of The fabric provides shades. The relative hue angle can be determined by any suitable method known in the art. Preferably, however, it can be determined as described in further detail herein for the deposition of leuco moieties on cottons relative to cottons in the absence of any leuco moieties.

As mentioned above, in a second embodiment, the present invention provides a laundry care composition comprising a laundry care ingredient and a leuco composition as described herein. The laundry care composition may comprise any suitable leuco composition or combination of leuco compositions described herein. The laundry care composition may contain any suitable laundry care ingredients. Laundry care ingredients suitable for use in the present invention are described in detail below.

Laundry Care Ingredients

The laundry care compositions may contain other suitable adjuvants, which in some aspects may be incorporated in whole or in part. Adjuvants can be selected according to the intended function of the laundry care composition. The first composition may contain adjuvants. In some aspects, in the case of a multi-compartment unit-dose article, the adjuvant may be a non-first (eg, second, third, fourth) encapsulated in a separate compartment from the first composition etc.) part of the composition. The non-first composition may be any suitable composition. Non-first compositions may be in the form of solids, liquids, dispersions, gels, pastes, or mixtures thereof. When a unit dose includes multiple compartments, the leuco colorant may be added to one or two or even all of the compartments, or the leuco colorant may be present in one or two or even all of the compartments. In one embodiment, the leuco colorant is added to a larger compartment, resulting in a lower concentration, which can minimize any problems related to potential contact staining. On the other hand, concentrating antioxidants with leuco colorants in smaller volume compartments can result in higher local concentrations of antioxidants, which can provide enhanced stability. Thus, the position and amount of leuco colorant can be selected by the formulator according to the desired properties of the unit dose, as understood by those skilled in the art.

adjuvant

Laundry care compositions may contain surfactant systems. The laundry care composition may comprise from about 1% to about 80% by weight of the laundry care composition, or from 1% to about 60% by weight, preferably from about 5% to about 50% by weight, more preferably about 8% to about 40% by weight of the surfactant system.

Surfactants: Suitable surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and amphoteric surfactants and mixtures thereof. Suitable surfactants can be linear or branched, substituted or unsubstituted, and can be derived from petrochemical or biological materials. Preferred surfactant systems contain both anionic and nonionic surfactants, preferably in a weight ratio of 90:1 to 1:90. In some cases, it is preferred that the weight ratio between the anionic surfactant and the nonionic surfactant is at least 1:1. However, ratios below 10:1 may be preferred. When present, total surfactant content levels are preferably 0.1% to 60%, 1% to 50%, or even 5% to 40% by weight of the subject composition.

Anionic surfactants: Anionic surfactants include, but are not limited to, organic hydrophobic groups containing typically 8 to 22 carbon atoms or typically 8 to 18 carbon atoms in their molecular structure, and at least one water-solubilizing group (which are preferably selected from sulfonates, sulfates and carboxylates to form water-soluble compounds) those surface-active compounds. Typically, the hydrophobic group includes a C8-C22 alkyl group, or an acyl group. The surfactants are used in the form of water-soluble salts, and the salt-forming cations are generally selected from sodium, potassium, ammonium, magnesium, and single ions, of which the sodium cation is generally selected.

Anionic Surfactants and Adjuvants of the Present Invention Anionic co-surfactants may exist in acid form, and the acid form may be neutralized to form surfactant salts which are useful for use in detergents herein desired in the composition. Typical reagents for neutralization include metal counterion bases such as hydroxides such as NaOH or KOH. Other preferred agents for neutralizing the anionic surfactants and co-agents of the present invention in their acid forms include ammonia, amines, oligoamines or alkanolamines. Alkanolamines are preferred. Suitable non-limiting examples include monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art; for example, highly preferred alkanolamines include 2-amino-1-propanol, 1 - aminopropanol, monoisopropanolamine or 1-amino-3-propanol. Amine neutralization can be done to a full or partial degree, for example, part of the anionic surfactant mixture can be neutralized with sodium or potassium, and part of the anionic surfactant mixture can be neutralized with amines or alkanolamines.

供应的那些，或由Petresa以商品名

供应的那些；其它适当的LAB包括高的(high)2-苯基LAB，例如由Sasol以商品名

供应的那些。适当的阴离子表面活性剂是通过DETAL催化方法获得的烷基苯磺酸盐，尽管其它合成路线例如HF也可能是合适的。在一个方面中，使用LAS的镁盐。Suitable sulfonate surfactants include methyl ester sulfonates, alpha-olefin sulfonates, alkyl benzene sulfonates, especially alkyl benzene sulfonates, preferably C _10-13 alkyl benzene sulfonates . Suitable alkyl benzene sulfonates (LAS) can be obtained by sulfonation of commercially available linear alkyl benzenes (LAB), preferably by the above method. Suitable LABs include low (low) 2-phenyl LABs such as those sold by Sasol under the tradename

those supplied, or by Petresa under the trade name

those supplied; other suitable LABs include high 2-phenyl LABs such as those sold by Sasol under the tradename

those supplied. Suitable anionic surfactants are alkylbenzene sulfonates obtained by DETAL catalyzed methods, although other synthetic routes such as HF may also be suitable. In one aspect, the magnesium salt of LAS is used.

Suitable sulfate surfactants include alkyl sulfates, preferably _C8-18 alkyl sulfates, or predominantly _C12 alkyl sulfates.

Preferred sulfate surfactants are alkyl alkoxylated sulfates, preferably alkyl ethoxylated sulfates, preferably C _8-18 alkyl alkoxylated sulfates, preferably C _8-18 alkanes alkyl ethoxylated sulfate; preferably, the average degree of alkoxylation of the alkyl alkoxylated sulfate is 0.5 to 20, preferably 0.5 to 10; preferably, the alkyl alkoxylated sulfate is a _C8-18 alkyl ethoxylated sulfate having an average degree of ethoxylation of 0.5 to 10, preferably 0.5 to 5, more preferably 0.5 to 3. The alkyl alkoxylated sulfates may have a broad distribution of alkoxy groups or a peaked distribution of alkoxy groups.

Alkyl sulfates, alkyl alkoxylated sulfates and alkyl benzene sulfonates may be linear or branched, including 2-alkyl substituted or substituted or unsubstituted mid-chain branched types, And can be derived from petrochemical materials or biological materials. Preferably, the branching group is an alkyl group. Typically, the alkyl group is selected from methyl, ethyl, propyl, butyl, pentyl, cycloalkyl, and mixtures thereof. One or more alkyl branches may be present on the main hydrocarbyl chain of one or more of the starting alcohols used to produce the sulfated anionic surfactants used in the detergents of the present invention. Most preferably, the branched sulfated anionic surfactant is selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, and mixtures thereof.

Alkyl sulfates and alkyl alkoxy sulfates are commercially available with various chain lengths, degrees of ethoxylation and branching. Commercially available sulfates include those based on Neodol alcohols from Shell, Lial-Isalchem and Safol from Sasol, natural alcohols from Procter & Gamble Chemicals.

Huntsman

和Clariant

获得。Other suitable anionic surfactants include alkyl ether carboxylates including C10-C26 linear or branched, preferably C10-C20 linear, most preferably C16-C18 linear alkyl alcohols and 2 to 20 , preferably 7 to 13, more preferably 8 to 12, most preferably 9.5 to 10.5 ethoxylates. Acid or salt forms, such as sodium or ammonium salts, may be used; and the alkyl chain may contain a cis or trans double bond. Alkyl ether carboxylic acids are available from Kao

Huntsman

and Clariant

get.

非离子表面活性剂；C₆-C₁₂烷基苯酚烷氧基化物，其中优选地，烷氧基化物单元是乙烯氧单元、丙烯氧单元或它们的混合物；C₁₂-C₁₈醇和C₆-C₁₂烷基苯酚与环氧乙烷/环氧丙烷嵌段聚合物的缩合物，例如来自BASF的

烷基多糖，优选地烷基多糖苷；甲酯乙氧基化物；多羟基脂肪酸酰胺；醚封端聚(氧烷基化)醇表面活性剂；及其混合物。Nonionic surfactants: Suitable nonionic surfactants are selected from: _C8 - _C18 alkyl ethoxylates, eg from Shell

Nonionic surfactants; C ₆ -C ₁₂ alkylphenol alkoxylates, wherein preferably the alkoxylate units are ethylene oxide units, propylene oxide units or mixtures thereof; C ₁₂ -C ₁₈ alcohols and C ₆ - Condensates _of C12-alkylphenols with ethylene oxide/propylene oxide block polymers, e.g. from BASF

Alkyl polysaccharides, preferably alkyl polyglycosides; methyl ester ethoxylates; polyhydroxy fatty acid amides; ether terminated poly(oxyalkylated) alcohol surfactants; and mixtures thereof.

Suitable nonionic surfactants are alkyl polyglycosides and/or alkyl alkoxylated alcohols.

购自BASF的那些。Suitable nonionic surfactants include alkyl alkoxylated alcohols, preferably C _8-18 alkyl alkoxylated alcohols, preferably C _8-18 alkyl ethoxylated alcohols; preferably, the alkane The average degree of alkoxylation of the alkyl alkoxylated alcohol is 1 to 50, preferably 1 to 30, or 1 to 20, or 1 to 10; preferably, the alkyl alkoxylated alcohol is an average ethoxylated alcohol _C8-18 alkyl ethoxylated alcohols with a degree of alkylation of 1 to 10, preferably 1 to 7, more preferably 1 to 5 and most preferably 3 to 7. In one aspect, the alkyl alkoxylated alcohol is a C _12-15 alkyl ethoxylated alcohol with an average degree of ethoxylation of 7 to 10. The alkyl alkoxylated alcohols may be linear or branched, and may be substituted or unsubstituted. Suitable nonionic surfactants include those under the trade name

Those purchased from BASF.

Cationic Surfactants: Suitable cationic surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulfonium compounds, and mixtures thereof.

Preferred cationic surfactants are quaternary ammonium compounds having the general formula:

(R)(R ₁ )(R ₂ )(R ₃ )N ⁺ X ^-

wherein R is _a linear or branched, substituted or unsubstituted _C6-18 alkyl or alkenyl moiety, R1 and _R2 are independently selected from methyl or ethyl moieties, and _R3 is hydroxy, hydroxymethyl or a hydroxyethyl moiety, X is an anion that provides charge neutrality, preferred anions include: halides, preferably chlorides; sulfates; and sulfonates.

The fabric care compositions of the present invention may contain up to about 30% by weight of the composition, alternatively from about 0.01% to about 20% by weight, more alternatively from about 0.1% to about 20% by weight of a cationic surfactant. For the purposes of the present invention, cationic surfactants include those that can provide fabric care benefits. Non-limiting examples of useful cationic surfactants include: fatty amines, imidazoline quaternary ammonium salt materials, and quaternary ammonium surfactants, preferably N,N-bis(stearoyl-oxy-ethyl)N,N - Dimethylammonium chloride, N,N-bis(tallowoyl-oxy-ethyl)N,N-dimethylammonium chloride, N,N-bis(stearoyl-oxy-ethyl) N-(2-hydroxyethyl)N-methylammonium methylsulfate; 1,2bis(stearoyl-oxy)3trimethylammonium chloropropane; dialkylenedimethylammonium salts such as Dicanoladimethylammonium chloride, di(hard) tallow dimethylammonium chloride Alkyl-2-stearoyl imidazoline methyl sulfate; 1-tallow aminoethyl-2-tallow imidazoline; N,N"-dialkyldiethylenetriamine; N-(2-hydroxyl Ethyl)-1,2-ethylenediamine or the reaction product of N-(2-hydroxyisopropyl)-1,2-ethylenediamine with glycolic acid esterified with a fatty acid, wherein the fatty acid is (hydrogenated) ) tallow fatty acids, palm fatty acids, hydrogenated palm fatty acids, oleic acid, rapeseed fatty acids, hydrogenated rapeseed fatty acids; polyglycerol esters (PGE), oily sugar derivatives and wax emulsions, and mixtures thereof.

It will be appreciated that the combinations of softener actives disclosed above are suitable for use herein.

Amphoteric and Zwitterionic Surfactants: Suitable amphoteric or zwitterionic surfactants include amine oxides and/or betaines. Preferred amine oxides are alkyl dimethyl amine oxide or alkylamidopropyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxide, especially coco dimethyl amine oxide. The amine oxides can have linear or intermediate branched alkyl moieties. Typical linear amine oxides include water-soluble amine oxides containing one R1 C8-18 alkyl moiety and 2 R2 and R3 moieties selected from C1-3 alkyl and C1-3 hydroxyalkyl. Preferably, the amine oxide is characterized by the formula R1-N(R2)(R3)O, wherein R1 is C8-18 alkyl, and R2 and R3 are selected from methyl, ethyl, propyl, isopropyl, 2-hydroxy Ethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amine oxide surfactants may include, inter alia, linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxyethyldihydroxyethyl amine oxides.

Other suitable surfactants include betaines such as alkylbetaines, alkylamidobetaines, amidazoliniumbetaines, sulfobetaines (INCI Sultaines), and phosphobetaines.

leuco colorant thinner

等，以及它们的组合。在聚合物中，环氧乙烷与环氧丙烷共聚物可能是优选的。这些聚合物通常以与水的浊点为特征，这可以帮助将产物与水分离以除去不想要的水溶性杂质。环氧乙烷和环氧丙烷共聚物的实例包括但不限于BASF的PLURONIC系列聚合物以及Dow的TERGITOL^TM系列聚合物。当将隐色着色剂组合物掺入到洗衣护理组合物中时，这些聚合物也可以充当非离子表面活性剂。Another class of ingredients in the leuco colorant composition may be diluents and/or solvents. The purpose of the diluent and/or solvent is usually, but not limited to, improving the flowability of the leuco colorant and/or reducing the viscosity of the leuco colorant. Although water is generally the preferred diluent and/or solvent due to its low cost and non-toxicity, other solvents may also be used. Preferred solvents are low cost and low hazard solvents. Examples of suitable solvents include, but are not limited to, ethylene glycol, propylene glycol, glycerol, alkoxylated polymers such as polyethylene glycol, polypropylene glycol, copolymers of ethylene oxide and propylene oxide,

etc., and their combinations. Among the polymers, ethylene oxide and propylene oxide copolymers may be preferred. These polymers are often characterized by a cloud point with water, which can help separate the product from water to remove unwanted water-soluble impurities. Examples of ethylene oxide and propylene oxide copolymers include, but are not limited to, BASF's PLURONIC series of polymers and Dow's TERGITOL ^™ series of polymers. These polymers can also act as nonionic surfactants when leuco colorant compositions are incorporated into laundry care compositions.

The laundry care compositions described herein may also include one or more of the following non-limiting ingredients: fabric care benefit agents; detergency enzymes; deposition aids; rheology modifiers; Lotions; chelating agents; bleaching agents; decolorizing agents; bleach precursors; bleaching aids; bleaching catalysts; perfumes and/or perfume microcapsules; perfumed zeolites; starch encapsulated accords; Polyglycerol esters; brighteners; pearlescent agents; enzyme stabilization systems; scavengers, including fixatives for anionic dyes, complexing agents for anionic surfactants, and mixtures thereof; optical brighteners or optical brighteners agents; polymers, including but not limited to soil release polymers and/or soil suspending polymers; dispersants; antifoams; non-aqueous solvents; fatty acids; suds suppressors such as silicone suds suppressors; cationic starches; foam dispersants direct dyes; colorants; opacifiers; antioxidants; hydrotropes such as tosylate, cumene sulfonate, and naphthalene sulfonate; color speckle; colored beads, spheres, or extrudates ; Clay softener; Antibacterial agent. Additionally or alternatively, the composition may comprise a surfactant, a quaternary ammonium compound and/or a solvent system. Quaternary ammonium compounds may be present in fabric enhancer compositions, such as fabric softeners, and comprise quaternary ammonium cations, which are positively charged polyatomic ^{ions of the structure NR4+} _, where R is an alkyl or aryl group

Hue Adjusting Dyes

The composition may contain additional fabric shade modifiers. Suitable fabric shade modifiers include dyes, dye-clay conjugates and pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of Color Index (C.I. ) or mixtures thereof. Preferred dyes include alkoxylated azothiophene, solvent violet 13, acid violet 50 and direct violet 9.

聚合物着色剂(位于美国South Carolina的Spartanburg的美利肯公司(Milliken and Company))。在一个方面中，适当的染料和颜料包括小分子染料和聚合物染料。所述美学着色剂可以包括选自以下的至少一个生色团组分：吖啶、蒽醌、吖嗪、偶氮、苯并二呋喃、苯并二呋喃酮、类胡萝卜素、香豆素、菁蓝、二氮杂半菁蓝、二苯基甲烷、甲

半菁蓝、靛类、甲烷、次甲基、萘二甲酰亚胺、萘醌、硝基、亚硝基、噁嗪、吩噻嗪、酞菁(例如酞菁铜)、吡唑、吡唑啉酮、喹诺酮、均二苯代乙烯、苯乙烯基、三芳基甲烷(例如三苯甲烷)、呫吨及其混合物。Aesthetic colorants. The composition may contain one or more aesthetic colorants. Suitable aesthetic colorants include dyes, dye-clay conjugates, pigments and

Polymeric Colorant (Milliken and Company, Spartanburg, South Carolina, USA). In one aspect, suitable dyes and pigments include small molecule dyes and polymeric dyes. The aesthetic colorant may include at least one chromophore component selected from the group consisting of acridine, anthraquinone, azine, azo, benzodifuran, benzodifurone, carotenoid, coumarin, Cyanine, Diazahemicyanine, Diphenylmethane, Methyl

Hemicyanine, indigo, methane, methine, naphthalimide, naphthoquinone, nitro, nitroso, oxazine, phenothiazine, phthalocyanine (eg copper phthalocyanine), pyrazole, pyridine oxazolinones, quinolones, stilbene, styryl, triarylmethanes (eg triphenylmethane), xanthenes and mixtures thereof.

蓝色AH、

蓝色BB、

蓝色275、

蓝色297、

蓝色BB、青色15、

绿色101、

橙色272、

橙色255、

粉红色AM、

粉红色AMC、

粉红色ST、

紫色129、

紫色LS、

紫色291、

黄色FT、

蓝色Buf、

粉红色AM、

粉红色PV、酸性蓝80、酸性蓝182、酸性红33、酸性红52、酸性紫48、酸性紫126、酸性蓝9、酸性蓝1及其混合物。In one aspect of the present invention, aesthetic colorants include

blue AH,

blue BB,

blue 275,

blue 297,

Blue BB, Cyan 15,

green 101,

orange 272,

orange 255,

pink AM,

pink AMC,

pink ST,

purple 129,

Purple LS,

purple 291,

yellow FT,

Blue Buf,

pink AM,

Pink PV, Acid Blue 80, Acid Blue 182, Acid Red 33, Acid Red 52, Acid Violet 48, Acid Violet 126, Acid Blue 9, Acid Blue 1 and mixtures thereof.

Encapsulation. The composition may include an encapsulating material. In one aspect, an encapsulant comprises a core, a shell having inner and outer surfaces, wherein the shell encloses the core. The core may contain any laundry care adjuvant, although typically the core may contain a material selected from the group consisting of: fragrances; brighteners; shade adjusting dyes; insect repellents; silicones; waxes; flavors; vitamins; fabric softeners skin care agents (in one aspect, paraffin); enzymes; antibacterial agents; bleaching agents; sensates; polyvinyl alcohol, optionally with other comonomers; polystyrene; polyisoprene; polycarbonate; polyester; polyacrylate; polyamide plastic (in one aspect, the polyamide plastic may include polyureas, polyurethanes, and/or polyurea urethanes; in one aspect, the polyureas may include polyoxymethylene ureas and/or melamine formaldehyde); polyolefins; polysaccharides (in one aspect, the polysaccharides may including alginates and/or chitosan); gelatin; shellac; epoxy resins; vinyl polymers; water-insoluble inorganics; silicones; and mixtures thereof.

Preferred encapsulates include fragrances. Preferred encapsulates include a shell, which may include melamine formaldehyde and/or cross-linked melamine formaldehyde. Other preferred capsule bodies include polyacrylate based shells. A preferred encapsulant includes a core material and a shell, it is disclosed that the shell at least partially surrounds the core material. At least 75%, 85% or even 90% of the encapsulates may have a breaking strength of 0.2 to 10 MPa and benefit agent leakage based on the total initially encapsulated benefit agent of 0% to 20%, or even less than 10% or 5%. Preferably, at least 75%, 85% or even 90% of the encapsulant may have: (i) 1 to 80 microns, 5 to 60 microns, 10 to 50 microns, or even 15 to 40 microns micron particle size, and/or (ii) at least 75%, 85% or even 90% of the encapsulant may have a particle wall thickness of 30 nm to 250 nm, 80 nm to 180 nm, or even 100 nm to 160 nm. The formaldehyde scavenger can be used with the encapsulant, eg, in the capsule slurry and/or added to the composition before, during, or after the encapsulant is added to the composition. Suitable capsules can be prepared by following the teachings of USPA 2008/0305982A1; and/or USPA 2009/0247449A1. Alternatively, suitable capsules can be purchased from Appleton Papers Inc., Appleton, Wisconsin, USA.

In a preferred aspect, the composition may comprise a deposition aid, preferably in addition to the encapsulant. Preferred deposition aids are selected from cationic polymers and nonionic polymers. Suitable polymers include cationic starch, cationic hydroxyethyl cellulose, polyvinyl formaldehyde, locust bean gum, mannan, xyloglucan, tamarind gum, polyethylene terephthalate, and dimethyl phthalate. A polymer of aminoethyl methacrylate, optionally with one or more monomers selected from acrylic acid and acrylamide.

spices. Preferred compositions of the present invention include fragrances. Typically, the composition includes a fragrance comprising one or more fragrance raw materials selected from the group described in WO08/87497. However, any fragrance that can be used in laundry care compositions can be used. A preferred method of incorporating perfume into the compositions of the present invention is by encapsulating perfume particles comprising water-soluble hydroxyl compounds or melamine-formaldehyde or modified polyvinyl alcohol.

odor reducing material

The detergent compositions of the present disclosure may include malodor reducing materials. The material can reduce or even eliminate the perception of one or more malodors. These materials can be characterized by a calculated Malodor Reduction Value ("MORV") calculated according to the test method shown in WO2016/049389.

As used herein, "MORV" is the calculated malodor reduction value of the subject material. The MORV of a material indicates the ability of the material to reduce or even eliminate the perception of one or more malodors.

The detergent compositions of the present disclosure may comprise a total of about 0.00025% to about 0.5%, preferably about 0.0025% to about 0.1%, more preferably about 0.005% to about 0.075%, and most preferably about 0.01% by weight of the composition % to about 0.05% of one or more malodor reducing materials. The cleaning composition may include from about 1 to about 20 malodor reducing materials, more preferably 1 to about 15 malodor reducing materials, and most preferably 1 to about 10 malodor reducing materials.

One, some or each of the malodor reducing materials may have a MORV of at least 0.5, preferably 0.5 to 10, more preferably 1 to 10, most preferably 1 to 5. One, some or each of the malodor reducing materials may have a universal MORV that defines all MORV values >0.5 for the malodors tested as described herein. The sum of the malodor reducing materials may have a Blocker Index of less than 3, more preferably less than about 2.5, even more preferably less than about 2, and still more preferably less than about 1, and most preferably about 0 . The sum of the malodor reducing materials may have an average blocker index of about 3 to about 0.001.

In the detergent compositions of the present disclosure, the malodor reducing material may have a Fragrance Fidelity Index and/or a Fragrance Fidelity Index of less than 3, preferably less than 2, more preferably less than 1, and most preferably about 0 Average Fragrance Fidelity Index of 3 to about 0.001. As the Fragrance Fidelity Index decreases, the malodor-reducing material provides less and less odor impact while continuing to counteract the malodor.

The detergent compositions of the present disclosure may include fragrances. The weight ratio between the parts of the malodor reducing composition and the parts of the fragrance can be from about 1:20,000 to about 3000:1, preferably from about 1:10,000 to about 1,000:1, more preferably from about 5,000:1 to about 500:1, most preferably about 1:15 to about 1:1. As the ratio between the malodor reducing composition and the fragrance fraction tightens, the malodor reducing material provides less and less odor impact while continuing to counteract the malodor.

tannin

The detergent compositions of the present disclosure may include tannins. Tannins are polyphenol secondary metabolites of higher plants, or galloyl esters and their derivatives, in which the galloyl moiety or its derivatives are attached to a core of various polyols, catechins, and triterpenoids (gallate). tannins, ellagitannins and complex tannins), or they are oligomeric and polymeric proanthocyanidins (proanthocyanidis) that can have inter-flavan coupling and substitution patterns (condensed tannins). The detergent compositions of the present disclosure may include tannins selected from the group consisting of gallotannins, ellagitannins, complex tannins, condensed tannins, and combinations thereof.

polymer. The composition may include one or more polymers. Examples are optionally modified carboxymethylcellulose, poly(vinyl-pyrrolidone), poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(ethylene hydrocarbyl imidazole), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.

The composition may include one or more amphiphilic detersive polymers. The polymers have balanced hydrophilic and hydrophobic properties that allow them to remove grease particles from fabrics and surfaces. Suitable amphiphilic alkoxylated grease wash polymers include a core structure and a plurality of alkoxylate groups attached to the core structure. These may include alkoxylated polyalkyleneimines, especially ethoxylated polyethyleneimines or polyethyleneimines, with inner polyethylene oxide blocks and outer polypropylene oxide blocks. Typically, these may be incorporated into the compositions of the present invention in amounts of 0.005% to 10% by weight, typically 0.5% to 8% by weight.

The composition may include modified hexamethylenediamine. The modification of the hexamethylene diamine includes: (1) performing one or two alkoxylation modifications on each nitrogen atom of the hexamethylene diamine. The alkoxylation modifications include the substitution of hydrogen atoms on the nitrogen atoms of hexamethylenediamine into (poly)alkyleneoxy chains having an average of about 1 to about 40 alkoxy moieties per modification , wherein the terminal alkoxy moiety of the alkyleneoxy chain is terminated with hydrogen, C1-C4 alkyl, sulfate, carbonate, or mixtures thereof; (2) for each nitrogen atom of hexamethylenediamine One C1-C4 alkyl moiety substitution and one or two alkoxylation modifications are performed. Alkoxylation modifications involving the replacement of hydrogen atoms with (poly)alkyleneoxy chains having an average of from about 1 to about 40 alkoxy moieties per modification, wherein the terminal alkoxy of the alkyleneoxy chain The base moiety is terminated with hydrogen, C1-C4 alkyl, or a mixture thereof; or (3) a combination thereof

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, can be used to provide additional grease removal properties. Such materials are described in WO 91/08281 and PCT 90/01815. Chemically, these materials include polyacrylates with one ethoxy side chain per 7-8 acrylate units. The side chain has the formula -( _CH2CH2O ) _m ( _{CH2 ) nCH3} , where m is _2-3 and n is 6-12. The side chains are linked to the "backbone" ester of the polyacrylate to provide a "comb" like polymeric structure. The molecular weight can vary, but is generally in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight of the compositions herein.

Another suitable carboxylate polymer is a copolymer comprising: (i) 50% to less than 98% by weight of structural units derived from one or more monomers including carboxyl groups; (ii) 1 % to less than 49% by weight of structural units derived from one or more monomers including sulfonate moieties; (iii) 1% to 49% by weight of structural units derived from the group consisting of formulas (I) and (II) Structural units of one or more types of monomers containing ether bonds:

Formula (I):

Wherein, in formula (I), R ₀ represents a hydrogen atom or a CH ₃ group, R represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and X represents a number from 0 to 5, provided that when R is X represents a number from 1 to 5 when single bond, and R ₁ is a hydrogen atom or a C ₁ to C ₂₀ organic group;

Formula (II)

wherein, in formula (II), R ₀ represents a hydrogen atom or a CH ₃ group, R represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, X represents 0-5, and R ₁ is a hydrogen atom or C ₁ to C ₂₀ organic group.

It may be preferred that the polymer has a weight average molecular weight of at least 50 kDa, or even at least 70 kDa.

Other suitable polymers include amphiphilic graft copolymers. Preferred amphiphilic graft copolymers include: (i) a polyethylene glycol backbone; and (ii) at least one pendant group selected from polyvinyl acetate, polyvinyl alcohol, and mixtures thereof. A preferred amphiphilic graft copolymer is Sokalan HP22 supplied by BASF. Other suitable polymers include random graft copolymers, preferably polyvinyl acetate grafted polyethylene oxide copolymers having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is preferably about 6000 and the weight ratio of polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 graft per 50 ethylene oxide units point. Typically, these are incorporated into the compositions of the present invention in amounts of 0.005% to 10% by weight, more typically 0.05% to 8% by weight.

The composition may include one or more soil release polymers. Examples include soil release polymers having structures defined by one of the following formulae (VI), VII) or (VIII):

(VI)-[(OCHR ¹ -CHR ² ) _a -O-OC-Ar-CO-] _d

(VII)-[(OCHR ³ -CHR ⁴ ) _b -O-OC-sAr-CO-] _e

(VIII)-[(OCHR ⁵ -CHR ⁶ ) _c -OR ⁷ ] _f

in:

a, b and c are 1 to 200;

d, e and f are 1 to 50;

Ar is 1,4-substituted phenylene;

sAr is 1,3-substituted phenylene substituted with SO3Me at position ₅ ;

Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, wherein the alkyl group is a _C1 - _C18 alkane or C ₂ -C ₁₀ hydroxyalkyl, or a mixture thereof;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from H or C ₁ -C ₁₈ n-alkyl or iso-alkyl; and

R ⁷ is linear or branched C ₁ -C ₁₈ alkyl, or linear or branched C ₂ -C ₃₀ alkenyl, or cycloalkyl having 5 to 9 carbon atoms, or C ₈ -C ₃₀ aryl group, or C ₆ -C ₃₀ arylalkyl.

Suitable soil release polymers are polyester soil release polymers such as Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6 supplied by Rhodia. Other suitable soil release polymers include Texcare polymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN300 and SRN325 available from Clariant. Other suitable soil release polymers are Marloquest polymers, such as Marloquest SL supplied by Sasol.

The composition may also include one or more cellulosic polymers including cellulose selected from the group consisting of alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose polymer. Preferred cellulosic polymers are selected from the group consisting of carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose and mixtures thereof. In one aspect, the carboxymethyl cellulose has a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da.

Soil Release Polymer: The composition may include a soil release polymer. Suitable soil release polymers have a structure defined by one of the following formulae (I), (II) or (III):

(I)-[(OCHR ¹ -CHR ² ) _a -O-OC-Ar-CO-] _d

(II)-[(OCHR ³ -CHR ⁴ ) _b -O-OC-sAr-CO-] _e

(III)-[(OCHR ⁵ -CHR ⁶ ) _c -OR ⁷ ] _f

in:

a, b and c are 1 to 200;

d, e and f are 1 to 50;

Ar is 1,4-substituted phenylene;

sAr is 1,3-substituted phenylene substituted with SO3Me at position ₅ ;

Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, wherein the alkyl group is a _C1 - _C18 alkane or C ₂ -C ₁₀ hydroxyalkyl, or a mixture thereof;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from H or C ₁ -C ₁₈ n-alkyl or iso-alkyl; and

R ⁷ is linear or branched C ₁ -C ₁₈ alkyl, or linear or branched C ₂ -C ₃₀ alkenyl, or cycloalkyl having 5 to 9 carbon atoms, or C ₈ -C ₃₀ aryl group, or C ₆ -C ₃₀ arylalkyl.

系列聚合物出售，例如

SRN240和

SRA300。其它适当的去污聚合物由索尔维公司(Solvay)以

系列聚合物出售，例如

SF2和

Crystal。Suitable soil release polymers are available from Clariant as

A series of polymers are sold, such as

SRN240 and

SRA300. Other suitable soil release polymers are available from Solvay as

A series of polymers are sold, such as

SF2 and

Crystal.

Known polymeric soil release agents, hereinafter referred to as "SRA" or "SRA's", may optionally be used in the detergent compositions of the present invention. If used, SRA will generally comprise from 0.01% to 10.0% by weight of the composition, usually from 0.1% to 5%, preferably from 0.2% to 3.0%.

Preferred SRAs generally have hydrophilic segments that hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and deposit on the hydrophobic fibers and remain adhered to them through the completion of the wash and rinse cycle, thereby A hydrophobic segment that serves as an anchor for the hydrophilic segment. This can make stains produced after treatment with SRA easier to clean in subsequent wash cycles.

SRAs can include, for example, various charged, such as anionic or even cationic (see US Pat. No. 4,956,447) monomer units, as well as uncharged monomer units, and the structure can be linear, linear, or even star-shaped of. They may include capping moieties that are particularly effective in controlling molecular weight or altering physical or surface active properties. The structure and charge distribution can be adjusted for different fiber or textile types and various detergent or detergent additive products. Suitable soil release polymers are polyester soil release polymers such as Repel-o-tex polymers, including Repel-o-tex, SF-2 and SRP6 supplied by Rhodia. Other suitable soil release polymers include Texcare polymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN300 and SRN325 available from Clariant. Other suitable soil release polymers are Marloquest polymers, such as Marloquest SL supplied by Sasol. SRA的实例在第4,968,451、4,711,730、4,721,580、4,702,857、4,877,896、3,959,230、3,893,929、4,000,093、5,415,807、4,201,824、4,240,918、4,525,524、4,201,824、4,579,681和4,787,989号美国专利，以及第0 219 048、279,134A、457,205A和It is described in European patent application DE 2,335,044.

Carboxylate polymer: The composition may include a carboxylate polymer, such as a maleate/acrylate random copolymer or a polyacrylate homopolymer. Suitable carboxylate polymers include: polyacrylate homopolymers having a molecular weight of 4,000 Da to 9,000 Da; and maleate/acrylate random copolymers having a molecular weight of 50,000 Da to 100,000 Da, or 60,000 Da to 80,000 Da thing.

Alternatively, these materials may include polyacrylates having one ethoxy side chain per 7-8 acrylate units. The side chain has the formula -( _CH2CH2O ) _m ( _{CH2 ) nCH3} , where m is _2-3 and n is 6-12. The side chains are linked to the "backbone" ester of the polyacrylate to provide a "comb" like polymeric structure. The molecular weight can vary, but is generally in the range of about 2000 to about 50,000. The alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight of the compositions herein.

Another suitable carboxylate polymer is a copolymer comprising: (i) 50% to less than 98% by weight of structural units derived from one or more monomers including carboxyl groups; (ii) 1 % to less than 49% by weight of structural units derived from one or more monomers including sulfonate moieties; (iii) 1% to 49% by weight of structural units derived from the group consisting of formulas (I) and (II) Structural units of one or more types of monomers containing ether bonds:

Formula (I):

Wherein, in formula (I), R ₀ represents a hydrogen atom or a CH ₃ group, R represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and X represents a number from 0 to 5, provided that when R is X represents a number from 1 to 5 when single bond, and R ₁ is a hydrogen atom or a C ₁ to C ₂₀ organic group;

Formula (II)

wherein, in formula (II), R ₀ represents a hydrogen atom or a CH ₃ group, R represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, X represents 0-5, and R ₁ is a hydrogen atom or C ₁ to C ₂₀ organic group.

It may be preferred that the polymer has a weight average molecular weight of at least 50 kDa, or even at least 70 kDa.

The carboxylate-based polymers may advantageously be used at a concentration of from about 0.1% to about 7% by weight of the compositions herein. Suitable polymeric dispersants include carboxylate polymers such as maleate/acrylate random copolymers or polyacrylate homopolymers. Preferably, the carboxylate polymer is a polyacrylate homopolymer having a molecular weight of 4,000 Daltons to 9,000 Daltons, or a maleate/acrylate copolymer having a molecular weight of 60,000 Daltons to 80,000 Daltons . Polymeric polycarboxylates and polyethylene glycols can also be used. The polyalkylene glycol-based graft polymer can be prepared from a polyalkylene glycol-based compound and a monomeric material, wherein the monomeric material includes a carboxyl group-containing monomer and optionally other monomers. Optional other monomers not classified as carboxyl-containing monomers include sulfonic acid-containing monomers, amino-containing monomers, allylamine monomers, quaternized allylamine monomers, N-ethylenyl monomers, Hydroxy monomers, vinyl aryl monomers, isobutylene monomers, vinyl acetate monomers, salts of any of these salts, derivatives of any of these salts, and mixtures thereof. While not intending to be bound by theory, it is believed that, when used in combination with other builders, including lower molecular weight polycarboxylates, polymeric dispersants act through crystal dispersion inhibition, particle detergency peptization, and anti-regeneration Precipitation to enhance the overall performance of detergent builders. Examples of polymeric dispersants can be found in US Patent No. 3,308,067, and European Patent Application Nos. 66915, EP 193,360 and EP 193,360.

Alkoxylated polyamine-based polymers: The composition may include an alkoxylated polyamine. Such materials include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylenediamine, and sulfated forms thereof. Also included are polypropoxylated derivatives. Various amines and polyalkyleneimines can be alkoxylated to varying degrees, and optionally further modified to provide the aforementioned benefits. A working example is the ethoxylation of a 600 g/mol polyethyleneimine core to 20 EO groups per NH and is available from BASF.

Useful alkoxylated polyamine-based polymers include alkoxylated polyethyleneimine types, wherein the alkoxylated polyalkyleneimine has a polyalkyleneimine core, polyalkyleneimine One or more side chains of the amine core are bonded to at least one nitrogen atom in the polyalkyleneimine core, wherein the alkoxylated polyalkyleneimine has empirical formula (I), i.e. (PEI) _a -(EO) _b -R ₁ , where a is the average number average molecular weight (MW _PEI ) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine, and is in the range of 100 to 100,000 Daltons where b is the average degree of ethoxylation of the one or more side chains of the alkoxylated polyalkyleneimine, and is in the range of ₅ to 40, and wherein R is independently selected From hydrogen, _C1 - _C4 alkyl, and combinations thereof.

Other suitable alkoxylated polyalkylene imines include those wherein the alkoxylated polyalkylene imine has a polyalkylene imine core, one or more of the polyalkylene imine core One side chain is bonded to at least one nitrogen atom in the polyalkyleneimine core, wherein the alkoxylated polyalkyleneimine has the empirical formula (II), i.e. (PEI) _o- (EO) _m ( PO) _{n -} R2 or (PEI) _o- (PO) _n (EO) _{m -} R2, where o is the average number average molecular weight of the polyalkyleneimine core of the alkoxylated polyalkyleneimine (MW _PEI ), and in the range of 100 to 100,000 Daltons, where m is the average degree of ethoxylation in the one or more side chains of the alkoxylated polyalkyleneimine, at 10 in the range of 1 to 50, wherein n is the average degree of propoxylation in the one or more side chains of the alkoxylated polyalkyleneimine, in the range of ₁ to 50, and wherein R independently is selected from hydrogen, _C1 - _C4 alkyl, and combinations thereof.

Amphiphilic graft copolymers: According to the present invention, amphiphilic graft copolymers can also be used. Particularly useful polymers include polymers having (i) a polyethylene glycol backbone; and (ii) at least one pendant moiety selected from polyvinyl acetate, polyvinyl alcohol, and mixtures thereof, also useful in the present invention. Suitable polyethylene glycol polymers include random graft copolymers comprising: (i) a hydrophilic backbone comprising polyethylene glycol; (ii) hydrophobic side chains selected from the group consisting of: _{C4- C25} alkyl, polypropylene, polybutene, vinyl esters of saturated _C1 - _C6 monocarboxylic acids, _C1 - _C6 alkyl esters of acrylic acid or methacrylic acid, and mixtures thereof. Suitable polyethylene glycol polymers have a polyethylene glycol backbone with randomly grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone may be in the range of 2,000 Da to 20,000 Da, or in the range of 4,000 Da to 8,000 Da. The molecular weight ratio between the polyethylene glycol backbone and the polyvinyl acetate side chains may be in the range of 1:1 to 1:5, or 1:1.2 to 1:2. The average number of grafting sites per ethylene oxide unit may be less than 1 or less than 0.8, the average number of grafting sites per ethylene oxide unit may be in the range of 0.5 to 0.9, or the average number of grafting sites per ethylene oxide unit The average number of grafting sites can be in the range of 0.1 to 0.5, or 0.2 to 0.4. A suitable polyethylene glycol polymer is Sokalan HP22. Suitable polyethylene glycol polymers are described in WO08/007320.

Cellulosic polymers: Cellulosic polymers can be used in accordance with the present invention. Suitable cellulosic polymers are selected from the group consisting of alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose, sulfoalkyl cellulose, more preferably selected from In carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

A suitable carboxymethyl cellulose has a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da.

Suitable carboxymethylcelluloses have a degree of substitution greater than 0.65 and a degree of blockiness greater than 0.45, eg as described in WO09/154933.

GDA商售的羧甲基纤维素，疏水改性羧甲基纤维素，例如CPKelco公司以

SH1商售的羧甲基纤维素的烷基烯酮二聚体衍生物，或者CPKelco公司以

V商售的嵌段羧甲基纤维素。The consumer product of the present invention may also include one or more cellulosic polymers including those selected from the group consisting of alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose Cellulose polymer. In one aspect, the cellulosic polymer is selected from the group consisting of carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixtures thereof. In one aspect, the carboxymethyl cellulose has a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da. An example of a carboxymethyl cellulose polymer is manufactured by the company CPKelko under the

Carboxymethyl cellulose, hydrophobically modified carboxymethyl cellulose, commercially available from GDA, such as CPKelco as

Alkyl ketene dimer derivatives of carboxymethyl cellulose commercially available from SH1, or CPKelco as

V commercially available block carboxymethyl cellulose.

Cationic polymers: Cationic polymers can be used in accordance with the present invention. A suitable cationic polymer will have at least 0.5 meq/gm, in another embodiment at least 0.9 meq/gm, in another embodiment at least 1.2 meq/gm, in yet another embodiment at the pH at which the composition is intended to be used A cationic charge density of at least 1.5 meq/gm in an embodiment, but also less than 7 meq/gm in one embodiment, and less than 5 meq/gm in another embodiment, the pH is generally in the range of pH 3 to pH 9, at In one embodiment in the range of pH 4 to pH 8. Here, the "cationic charge density" of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. The average molecular weight of such suitable cationic polymers will typically be 10,000 to 10 million, in one embodiment 50,000 to 5 million, and in another embodiment 100,000 to 3 million.

Suitable cationic polymers for use in the compositions of the present invention contain cationic nitrogen-containing moieties, such as quaternary ammonium or cationic protonated amino moieties. Any anionic counterion can be used in conjunction with the cationic polymer as long as the polymer remains water soluble, soluble in the composition, or soluble in the coacervate of the composition, and as long as the counterion is physically and It is sufficient that it is chemically compatible with the essential components of the composition or does not unduly impair the performance, stability or aesthetics of the product. Non-limiting examples of such counterions include halides (eg, chloride, fluoride, bromide, iodide), sulfate, and methyl sulfate.

Non-limiting examples of such polymers are found in the CTFA Cosmetic Ingredient Dictionary, 3rd Edition, edited by Estrin, Crosley, and Haynes (The Cosmetic, Toiletry, and Fragrance Association), Washington, DC, USA. (1982)).

Particularly effective cationic polymers that can be used in accordance with the present invention include wherein the cationic polymer includes a polymer selected from the group consisting of cationic cellulose, cationic guar, poly(acrylamide-co-diallyldimethyl) ammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid), poly(propylene Amide-co-methacrylamidopropyl-pentamethyl-1,3-propen-2-ol-ammonium dichloride), poly(acrylamide-co-N,N-dimethylaminoethyl acrylic acid) ester) and its quaternized derivatives, poly(acrylamide-co-N,N-dimethylaminoethyl methacrylate) and its quaternized derivatives, poly(acrylamide-methacrylamido) propyltrimethylammonium chloride), poly(acrylamide-methacrylamidopropyltrimethylammonium chloride-co-acrylic acid), poly(diallyldimethylammonium chloride), poly( Diallyldimethylammonium chloride-co-acrylic acid), poly(ethyl methacrylate-co-oleyl methacrylate-co--diethylaminoethyl methacrylate) and their Quaternized derivatives, poly(ethyl methacrylate-co-dimethylaminoethyl methacrylate) and their quaternized derivatives, poly(hydroxypropyl acrylate-co-methacrylate amides) propyltrimethylammonium chloride) and its quaternized derivatives, poly(hydroxyethyl acrylate-co-dimethylaminoethyl methacrylate) and its quaternized derivatives, poly(methyl methacrylate) Acrylamide-co-dimethylaminoethyl acrylate) and its quaternized derivatives, poly(methacrylate-co-methacrylamidopropyltrimethyl ammonium chloride), poly(ethylene Alkylformamide-co-acrylic acid-co-diallyldimethylammonium chloride), poly(vinylformamide-co-diallyldimethylammonium chloride), poly(vinylpyrrolidone-co- - Acrylamide-co-ethylenyl imidazole) and its quaternized derivatives, poly(ethylenyl pyrrolidone-co-dimethylaminoethyl methacrylate) and its quaternized derivatives, poly(ethylenyl pyrrolidone - co-methacrylic acid amide-co-ethylenyl imidazole) and its quaternized derivatives, poly(ethylenyl pyrrolidone-co-ethylenyl imidazole) and its quaternized derivatives, polyethyleneimine, and including its Quaternized derivatives and mixtures thereof

Other suitable cationic polymers for use in the compositions include polysaccharide polymers, cationic guar gum derivatives, tetravalent nitrogen-containing cellulose ethers, synthetic polymers, etherified celluloses, copolymers of guar gum and starch . When used, the cationic polymers herein are soluble in the composition, or in the complex coacervate phase of the composition formed from the cationic polymer described above and the anionic, amphoteric and/or zwitterionic surfactant components . Complex coacervates of cationic polymers can also be formed with other charged materials in the composition.

Suitable cationic polymers are described in US Pat. Nos. 3,962,418, 3,958,581, and US Publication No. 2007/0207109A1.

HP 56K、

HP 66。染料控制剂可以选自(i)磺化苯酚/甲醛聚合物；(ii)尿素衍生物；(iii)烯键式不饱和单体的聚合物，其中该聚合物被染料在分子上压印；(iv)由不溶于水的聚酰胺组成的纤维，其中所述纤维的平均直径不大于约2μm；(v)可通过使苯并恶嗪单体化合物聚合而获得的聚合物；以及(vi)它们的组合物。其它适当的DTI如WO2012/004134中所述。当存在于对象组合物中时，染料转印抑制剂按组合物的重量计，可以以0.0001％到约10％，约0.01％到约5％或者甚至约0.1％到约3％的浓度存在。Dye Transfer Inhibitor (DTI). The composition may include one or more dye transfer inhibitors. In one embodiment of the present invention, the inventors have surprisingly found that compositions comprising polymeric dye transfer inhibitors in addition to the specified dyes have improved properties. This is surprising because these polymers prevent dye deposition. Suitable dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-ethylenylpyrrolidone and N-ethylenylimidazole, polyvinyloxazolidinone and polyvinyl oxazolidinone. Ethylimidazole or mixtures thereof. Suitable examples include PVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and Chromabond S-100 sold by Ashland Aqualon, and Sokalan HP165, Sokalan HP50, Sokalan HP53, Sokalan HP59 sold by BASF ,

HP 56K,

HP 66. Dye control agents may be selected from (i) sulfonated phenol/formaldehyde polymers; (ii) urea derivatives; (iii) polymers of ethylenically unsaturated monomers, wherein the polymers are molecularly imprinted by dyes; (iv) fibers composed of water-insoluble polyamides, wherein the fibers have an average diameter of not greater than about 2 μm; (v) polymers obtainable by polymerizing benzoxazine monomer compounds; and (vi) their composition. Other suitable DTIs are described in WO2012/004134. When present in the subject composition, the dye transfer inhibitor can be present at a concentration of 0.0001% to about 10%, about 0.01% to about 5%, or even about 0.1% to about 3% by weight of the composition.

Other water-soluble polymers: Examples of water-soluble polymers include, but are not limited to, polyvinyl alcohol (PVA), modified PVA; polyvinylpyrrolidone; PVA copolymers such as PVA/polyvinylpyrrolidone and PVA/polyvinylamine ; partially hydrolyzed polyvinyl acetate; polyoxyalkylenes, such as polyethylene oxide; polyethylene glycol; acrylamide; acrylic acid; cellulose, alkyl cellulose, such as methyl cellulose, ethyl cellulose and propylene cellulose; cellulose ethers; cellulose esters; cellulose amides; polyvinyl acetates; polycarboxylic acids and salts; polyamino acids or peptides; polyamides; polyacrylamides; copolymers of maleic/acrylic acid; polysaccharides , including starch, modified starch; gelatin; alginate; xyloglucan, other hemicellulose polysaccharides, including xylan, glucuronic acid xylan, arabinoxylan, mannan, glucomannan polysaccharides and galactoglucomannans; and natural gums such as pectin, xanthan and carrageenan, locust bean gum, acacia, tragacanth; and combinations thereof

Non-limiting examples of amines include, but are not limited to, etheramines, cyclic amines, polyamines, oligoamines (eg, triamines, diamines, pentylamines, tetraamines), or combinations thereof. The compositions described herein can include amines selected from the group consisting of oligomeric amines, ether amines, cyclic amines, and combinations thereof. In some aspects, the amine is not an alkanolamine. In some aspects, the amine is not a polyalkyleneimine.

Examples of suitable oligomeric amines include tetraethylenepentamine, triethylenetetramine, diethylenetriamine, and mixtures thereof.

Etheramines: The detergent compositions described herein may include etheramines. The cleaning composition may contain from about 0.1% to about 10%, from about 0.2% to about 5%, or from about 0.5% to about 4% etheramine by weight of the composition.

The ether amines of the present disclosure may have a weight average molecular weight of less than about 1000 g/mole, or about 100 g/mole to about 800 g/mole, or about 200 g/mole to about 450 g/mole, or about 290 g/mole to about About 1000 g/mole, or about 290 g/mole to about 900 g/mole, or about 300 g/mole to about 700 g/mole, or about 300 g/mole to about 450 g/mole. The weight average molecular weight of the etheramines of the present invention can be from about 150 grams/mole, or from about 200 grams/mole, or from about 350 grams/mole, or from about 500 grams/mole, to about 1000 grams/mole, or to about 900 g/mole, or to about 800 g/mole.

Alkoxylated phenolic compounds: The detergent compositions of the present disclosure may include alkoxylated phenolic compounds. The alkoxylated phenolic compound may be selected from alkoxylated polyarylphenolic compounds, alkoxylated polyalkylphenolic compounds, and mixtures thereof. The alkoxylated phenolic compound may be an alkoxylated polyarylphenolic compound. The alkoxylated phenol compound may be an alkoxylated polyalkylphenol compound.

The alkoxylated phenolic compound may be present in the detergent composition at a concentration of from about 0.2% to about 10%, or from about 0.5% to about 5%, by weight of the detergent composition.

The weight average molecular weight of the alkoxylated phenolic compound may be between 280 and 2880.

enzymes. Preferably, the composition comprises one or more enzymes. Preferred enzymes provide wash performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, Pectate lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, lignase, pullulanase, tannase, pentosanase, malanase, Beta-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase and amylase, or mixtures thereof. A typical combination is an enzyme mixture that may include, for example, a combination of protease and lipase and amylase. When present in the composition, the aforementioned additional enzymes may be present at a concentration of about 0.00001% to about 2%, about 0.0001% to about 1%, or even about 0.001% to about 0.5% enzyme protein by weight of the composition .

Proteases Preferably, the composition includes one or more proteases. Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, the suitable protease may be of microbial origin. Suitable proteases include chemically or genetically modified mutants of the appropriate proteases described above. In one aspect, suitable proteases may be serine proteases, such as alkaline microbial proteases or/and trypsin-type proteases. Examples of suitable neutral or alkaline proteases include:

(a) Subtilisins (EC 3.4.21.62), including subtilisins derived from Bacillus, eg Bacillus lentus described in US 6,312,936B1, US 5,679,630, US 4,760,025, US 7,262,042 and WO09/021867 lentus), B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii.

(b) Trypsin-type or chymotrypsin-type proteases, such as proteases (eg, trypsin of porcine or bovine origin), including the Fusarium protease described in WO 89/06270 and WO 05/052161 and chymotrypsin derived from Cellumonas as described in WO 05/052146.

(c) Metalloproteases, including metalloproteases derived from Bacillus amyloliquefaciens as described in WO 07/044993 A2.

Preferred proteases include those derived from Bacillus gibsonii or Bacillus Lentus.

Liquanase

Savinase

和

出售的蛋白酶，美国杰能科酶制剂公司(Genencor International)以商品名

Purafect

Purafect

和Purafect

出售的蛋白酶，Solvay Enzymes公司以商品名

和

出售的蛋白酶，即可购自Henkel/Kemira公司的产品，即BLAP(序列号见US 5,352,604的图29，具有以下突变型S99D+S101 R+S103A+V104I+G159S(以下称为BLAP)、BLAP R(带有S3T+V4I+V199M+V205I+L217D的BLAP)、BLAP X(带有S3T+V4I+V205I的BLAP)和BLAP F49(带有S3T+V4I+A194P+V199M+V205I+L217D的BLAP)-全部来自Henkel/Kemira公司；以及来自花王公司(Kao)的KAP(具有突变型A230V+S256G+S259N的嗜碱芽孢杆菌枯草杆菌蛋白酶(Bacillus alkalophilus subtilisin))。Suitable commercially available proteases include Novozymes (Novozymes A/S, Denmark) under the trade name

Liquanase

Savinase

and

Protease sold under the trade name Genencor International

Purafect

Purafect

and Purafect

Protease sold under the trade name Solvay Enzymes

and

The protease for sale is a product that can be purchased from Henkel/Kemira company, namely BLAP (see Figure 29 of US 5,352,604 for the serial number), with the following mutants S99D+S101R+S103A+V104I+G159S (hereinafter referred to as BLAP), BLAP R (BLAP with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with S3T+V4I+V205I) and BLAP F49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D)- All from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with mutants A230V+S256G+S259N) from Kao.

Amylase Preferably, the composition may include an amylase. Suitable alpha-amylases include alpha-amylases of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. Preferred alkaline alpha-amylases are derived from strains of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis or other Bacillus species, such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (USP 7,153,818) DSM 12368, DSMZ No. 12649, KSM AP1378 (WO 97/00324), SMK36 or KSM K38 (EP 1,022,334). Preferred amylases include:

(a) Variants described in WO 94/02597, WO 94/18314, WO 96/23874 and WO 97/43424, especially with respect to the enzymes listed in SEQ ID No. 2 in WO 96/23874 in one of the following Variants with substitution at or multiple positions: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408 and 444.

(b) USP 5,856,164 and the variants described in WO 99/23211, WO 96/23873, WO 00/60060 and WO 06/002643, especially with respect to the AA560 enzyme set forth in SEQ ID No. 12 in WO 06/002643 , variants with one or more substitutions at:

26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, preferably also contain deletions of D183* and G184*.

(c) variants exhibiting at least 90% identity to SEQ ID No. 4 in WO06/002643, the wild-type enzyme from Bacillus sp722, especially variants with deletions at positions 183 and 184 and by reference The variants described in WO 00/60060 herein are incorporated by means.

(d) variants exhibiting at least 95% identity to the wild-type enzyme from Bacillus 707 (SEQ ID NO: 7 in US 6,093,562), especially including the following mutants M202, M208, S255, R172 and /or variants of one or more of M261. Preferably, the amylase comprises one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and/or R172Q. Particularly preferred are amylases comprising M202L or M202T mutants.

(e) the variant described in WO 09/149130, preferably exhibiting the same A variant of an enzyme or a truncated form thereof that is at least 90% identical.

TERMAMYL

STAINZYME

和

(维诺信公司(Novozymes A/S)，丹麦巴格思韦)、

AT 9000Biozym Biotech TradingGmbH Wehlistrasse 27b A-1200Wien Austria、

OPTISIZE HT

和PURASTAR

(美国杰能科酶制剂公司(Genencor International)美国加利福尼亚轴帕罗奥多(Palo Alto))和

(花王公司(Kao)，日本东京中央区一丁目日本桥茅场町14-10，邮编：103-8210)。在一个方面中，适当的淀粉酶包括

和STAINZYME

及其混合物。Suitable commercially available alpha-amylases include

TERMAMYL

STAINZYME

and

(Novozymes A/S, Bagsway, Denmark),

AT 9000Biozym Biotech TradingGmbH Wehlistrasse 27b A-1200Wien Austria,

OPTISIZE HT

and PURASTAR

(Genencor International, Palo Alto, California, USA) and

(Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku, Tokyo, Japan, 103-8210). In one aspect, suitable amylases include

and STAINZYME

and its mixtures.

和

和

出售的脂肪酶。Lipase. Preferably, the present invention includes one or more lipases, including "first cycle lipases" such as those described in US Pat. No. 6,939,702B1 and US PA 2009/0217464. Preferred lipases are first-wash lipases. In one embodiment of the invention, the composition comprises a first wash lipase. The lipase included in the first wash lipase is a polypeptide having the following amino acid sequence: (a) at least 90% identical to a wild-type lipase derived from Humicola lanuginosa strain DSM 4109; (b) with Compared to the wild-type lipase, electrically neutral or negatively charged amino acids on the surface of the three-dimensional structure included in 15A of E1 or Q249 are substituted with positively charged amino acids; (c) peptide additions including the C-terminus; and/or (d) includes N-terminal peptide addition, and/or (e) satisfies the following constraints: i) including the negative amino acid at position E210 of the wild-type lipase; ii) including the negative amino acid at position E210 of the wild-type lipase Negatively charged amino acids in the region corresponding to positions 90-101 of the lipase; iii) include neutral or negative amino acids at positions corresponding to N94 or the wild-type lipase, and/or have a position corresponding to the wild-type lipase Negative or neutral net charge in the region of position 90-101 of type lipase. Preferred are variants of the wild-type lipase from Thermomyces lanuginosa comprising one or more of the T231R and N233R mutants. The wild-type sequence is 269 amino acids (amino acids 23-291) of Swissprot Accession No. Swiss-Prot 059952 (derived from Humicola lanuginosa). Preferred lipases will include those under the trade name

and

and

Lipase for sale.

和

(维诺信公司(Novozymes A/S)，丹麦巴格思韦)出售。Endoglucanase. Other preferred enzymes include microbial-derived endoglucanases (EC 3.2.1.4) that exhibit endo-beta-1,4-glucanase activity, including endogenous bacterial polypeptides of members of the genus Bacillus , whose sequence is at least 90%, 94%, 97% and even 99% identical to the amino acid sequence SEQ ID NO: 2 in US 7,141,403B2) and mixtures thereof. Appropriate endoglucanases are available under the trade name

and

(Novozymes A/S, Bagsway, Denmark).

出售的果胶酸裂合酶，以及以商品名

(均来自维诺信公司(Novozymes A/S)，丹麦巴格思韦)和

(美国杰能科酶制剂公司(Genencor International)美国加利福尼亚轴帕罗奥多(Palo Alto))出售的甘露聚糖酶。Pectate lyase. Other preferred enzymes include those under the trade name

Pectate lyase sold under the trade name

(both from Novozymes A/S, Bagsway, Denmark) and

(Mannanase sold by Genencor International, Palo Alto, California, USA).

Nuclease. The composition may include a nuclease. Nucleases are enzymes capable of cleaving phosphodiester bonds between nucleotide subunits of nucleic acids. Nucleases herein are preferably deoxyribonucleases or ribonucleases or functional fragments thereof. A functional fragment or portion refers to the portion of the nuclease that catalyzes the cleavage of phosphodiester bonds in the DNA backbone, and thus is the region of the nuclease protein that retains catalytic activity. Thus, it includes truncated but functional forms of enzymes and/or variants and/or derivatives and/or homologs in which functionality is maintained.

Preferably, the nuclease is a deoxyribonuclease, preferably selected from the class E.C.3.1.21.x, where x=1, 2, 3, 4, 5, 6, 7, 8 or 9; E.C.3.1.22.y , where 1, 2, 4 or 5; E.C.3.1.30.z, where z=1 or 2; any of E.C.3.1.31.1 and mixtures thereof.

bleach. The composition may preferably include one or more bleaching agents. Suitable bleaching agents other than bleach catalysts include photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, and mixtures thereof. Typically, when a bleaching agent is used, the compositions of the present invention may comprise from about 0.1% to about 50%, or even from about 0.1% to about 25%, by weight of the subject composition, of a bleaching agent or mixture of bleaching agents. Examples of suitable bleaches include:

(1) Photobleaching agents such as sulfonated zinc phthalocyanine, sulfonated aluminum phthalocyanine, xanthene dyes, thioxanthone and mixtures thereof;

以及它们的混合物的化合物。(2) Preformed peracids: suitable preformed peracids include, but are not limited to, selected from preformed peroxyacids or salts thereof, typically percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, Peroxymonosulfuric acid and salts such as

and their mixtures.

Particularly preferred peroxyacids are phthalimido-peroxy-alkanoic acids, especially ε-phthalimido-peroxyhexanoic acid (PAP). Preferably, the melting point of the peroxyacid or its salt is in the range of 30°C to 60°C.

(3) Sources of hydrogen peroxide, such as inorganic perhydrate salts, including alkali metal salts, such as sodium salts of perborate (usually monohydrate or tetrahydrate), percarbonate, persulfate, Phosphates, persilicates and mixtures thereof. When used, inorganic perhydrate salts are typically present in amounts ranging from 0.05% to 40% by weight or from 1% to 30% by weight of the entire fabric and home care product, and are typically incorporated in the form of crystalline solids that can be coated into such fabrics and home care products. Suitable coatings include inorganic salts such as alkali metal silicates, carbonates or borates or mixtures thereof, or organic materials such as water-soluble or dispersible polymers, waxes, oils or fatty soaps; and

(4) Bleach activators having R-(C=O)-L, wherein R is an alkyl, optionally branched alkyl, having 6 to 14 carbons when the bleach activator is hydrophobic atoms or 8 to 12 carbon atoms, and when the bleach activator is hydrophilic, has less than 6 carbon atoms or even less than 4 carbon atoms; and L is a leaving group. An example of a suitable leaving group is benzoic acid and its derivatives, especially benzenesulfonate. Suitable bleach activators include dodecanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, decanoyloxybenzoic acid or a salt thereof, 3,5,5-trimethylhexanoyloxybenzene sulfonate, tetraacetylethylenediamine (TAED) and nonanoyloxybenzenesulfonate (NOBS).

(5) Bleach catalyst. The compositions of the present invention may also include one or more bleach catalysts capable of accepting and transferring oxygen atoms from peroxyacids and/or salts thereof to oxidizable substrates. Suitable bleach catalysts include, but are not limited to: imide cations and polyions; imine zwitterions; modified amines; modified amine oxides; Thiadiazide dioxide; perfluoroimine; cyclic sugar ketones and alpha amino ketones and mixtures thereof. A particularly preferred catalyst is an acylhydrazone type catalyst such as 4-(2-(2-((2-hydroxyphenylmethyl)methylene)hydrazino)-2-oxoethyl)-4-methyl base chloride.

(6) The composition may preferably include a catalytic metal complex. A preferred type of metal-containing bleach catalyst is a catalyst system comprising transition metal cations having defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations.

If desired, the compositions herein can be catalyzed by means of manganese compounds. Such compounds and use concentrations are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,576,282. In some embodiments, in the absence of other sources of oxidant in the composition, molecular oxygen from air provides the source of oxidation.

Cobalt bleach catalysts useful in the present invention are known and described, for example, in U.S. 5,597,936, U.S. 5,595,967.

When present, the source of hydrogen peroxide/peracid and/or bleach activator is typically from about 0.1% to about 60% by weight, from about 0.5% to about 40% by weight, or even about 0.6% by weight based on the fabric and home care product % to about 10% by weight are present in the composition. One or more hydrophobic peracids or precursors thereof may be used in combination with one or more hydrophilic peracids or precursors thereof.

Typically, the hydrogen peroxide source and bleach activator will be combined. The amounts of hydrogen peroxide source and peracid or bleach activator can be selected such that the molar ratio between available oxygen (from the peroxide source) to peracid is 1:1 to 35:1, or even 2:1 to 10 :1. If formulated as a liquid detergent, the peroxide source and activator can be formulated at low pH, typically at 3-5, with a pH jump system such as borate/sorbitol.

The laundry care compositions of the present invention are particularly useful in chlorinated water, such as commonly found in most household water supplies. Alternatively, the leuco-containing system can be used in combination with other bleaching sources, such as electrolysis, and can be used in a self-dosing system.

builder. Preferably, the composition may include one or more builders or builder systems. When a builder is used, the compositions of the present invention will generally comprise at least 1%, 2% to 60% builder. It may be preferred that the composition includes a low concentration of phosphate and/or zeolite, eg 1 to 10 or 5 wt%. The composition may even be substantially free of strong builders; substantially free of strong builders means "no intentional addition" of zeolites and/or phosphates. Typical zeolite builders include zeolite A, zeolite P and zeolite MAP. A typical phosphate builder is sodium tripolyphosphate.

Chelating agent. Preferably, the composition comprises a chelating agent and/or a crystal growth inhibitor. Suitable molecules include copper, iron and/or manganese chelating agents and mixtures thereof. Suitable molecules include hydroxamic acids, aminocarboxylates, aminophosphonates, succinates, salts thereof, and mixtures thereof. Non-limiting examples of suitable chelating agents suitable for use in the present invention include ethylenediaminetetraacetate, N-(hydroxyethyl)ethylenediaminetriacetate, nitrilotriacetate, ethylenediamine Ethylenediaminetetrapropionate, Triethylenetetraminehexaacetate, Diethylenetriaminepentaacetate, Ethanoldiglycine, Ethylenediaminetetra(methylenephosphonate), Diethylenediaminetetramine Ethylene triamine penta(methylene phosphonic acid) (DTPMP), ethylene diamine succinic acid ammonium salt (EDDS), hydroxyethane dimethylene phosphonic acid (HEDP), methylglycine diacetic acid ( MGDA), diethylenetriaminepentaacetic acid (DTPA), its salts and mixtures thereof. Other non-limiting examples of chelating agents useful in the present invention can be found in US Pat. Nos. 7,445,644, 7,585,376 and 2009/0176684A1. Other suitable chelating agents for use herein are the commercial DEQUEST series of chelating agents, as well as chelating agents from Monsanto, Dupont and Nalco, Inc. Other suitable chelating agents include pyridyl N-oxide types.

Fluorescent whitening agent. Preferably, the composition includes one or more optical brighteners. Commercially available optical brighteners useful in the present invention can be divided into subgroups including, but not limited to, derivatives of the following: stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanine Blue, dibenzothiophene-5,5-dioxide, pyrrole, five- and six-membered ring heterocycles, and other contaminants. Particularly preferred whitening agents are selected from: sodium 2(4-styrenehydrocarbyl-3-sulfophenyl)-2H-naphthanol[1,2-d]triazole, disodium 4,4'-bis{[ ((4-anilino-6-(N-methyl-N-2hydroxyethyl)amino1,3,5-triazin-2-yl)]amino}-2-2-disulfonate, disulfonate Sodium 4,4'-bis{[((4-anilino-6-morpholino-l,3,5-triazin-2-yl)]amino}stilbene-2-2'disulfonate , and disodium 4,4'-bis(2-sulfostyrene hydrocarbyl)biphenyl. Other examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents" )", M. Zahradnik, published by John Wiley & Sons, New York (1982). A specific non-limiting example of optical brighteners that can be used in the compositions of the present invention is US Pat. No. 4,790,856 and brighteners identified in US Pat. No. 3,646,015.

Preferred brighteners have the following structure:

Suitable concentrations of optical brightener include from a lower concentration of about 0.01 wt %, from about 0.05 wt %, from about 0.1 wt % or even from a lower concentration of about 0.2 wt % to an upper concentration of 0.5 wt % or even 0.75 wt %.

In one aspect, the whitening agent can be loaded onto the clay to form particles.

Preferred brighteners are wholly or predominantly (generally at least 50 wt%, at least 75 wt%, at least 90 wt%, at least 99 wt%) in the alpha-crystalline form. Highly preferred brighteners include C.I. Optical Brightener 260, preferably having the following structure:

This is particularly useful as it dissolves well in cold water, eg below 30°C or 25°C or even 20°C.

Enzyme Stabilizer. The composition may preferably include an enzyme stabilizer. Any conventional enzyme stabilizer can be used, for example, by the presence of a water-soluble source of calcium and/or magnesium ions in finished fabrics and home care products that provide these ions to the enzyme. In the case of aqueous compositions comprising proteases, reversible protease inhibitors may be added, such as boron compounds including borates or preferably 4-formylphenylboronic acid, phenylboronic acid and derivatives thereof, or compounds such as calcium formate , sodium formate and 1,2-propanediol to further improve stability.

solvent system. The solvent system in the composition of the present invention may be a solvent system containing only water, or a solvent system containing no water or a preferably water-containing organic solvent mixture.

Organic solvents

The composition may optionally include an organic solvent. Suitable organic solvents include _C4-14 ethers and diethers, glycols, alkoxylated glycols, _C6 - _C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols , alkoxylated aliphatic branched alcohols, alkoxylated linear C ₁ -C ₅ alcohols, linear C ₁ -C ₅ alcohols, amines, C ₈ -C ₁₄ alkyl and cycloalkyl hydrocarbons and halogenated Hydrocarbons and mixtures thereof. Preferred organic solvents include 1,2-propanediol, 2,3-butanediol, ethanol, glycerol, ethoxylated glycerol, dipropylene glycol, methylpropylene glycol, and mixtures thereof. Other lower alcohols, C1-C4 alkanolamines, such as monoethanolamine and triethanolamine, can also be used. Solvent systems may, for example, be absent from the anhydrous solid embodiments of the present invention, but are more typically from about 0.1% to about 98% by weight of the organic solvent liquid detergent composition, preferably at least about 1 % to about 50%, more typically about 5% to about 25%, or about 1% to about 10% concentration. These organic solvents can be used in combination with water or without water.

Structured Liquid: In some embodiments of the present invention, the composition is in the form of a structured liquid. The structured liquid may be internally structured whereby the structure is formed from primary components (eg surfactant materials) and/or through the use of secondary components (eg polymers, clays and/or silicate materials) A three-dimensional matrix structure is provided and externally structured, eg for use as a thickener. The composition may comprise a structurant, preferably from 0.01% to 5% by weight, from 0.1% to 2.0% by weight of a structurant. Examples of suitable structurants are found in US2006/0205631A1, US2005/0203213A1, US7294611, US6855680. The structurant is typically selected from the group consisting of di- and triglycerides, ethylene glycol distearate, microcrystalline cellulose, cellulose-based materials, microfibrous cellulose, hydrophobically modified alkali-swellable emulsions, such as Polygel W30 (3VSigma), biopolymers, xanthan gum, gellan gum, hydrogenated castor oil, derivatives of hydrogenated castor oil, such as non-ethoxylated derivatives thereof and mixtures thereof, specifically selected from hydrogenated castor oil Sesame oil, derivatives of hydrogenated castor oil, microfibrous cellulose, hydroxy-functional crystalline materials, long-chain fatty alcohols, 12-hydroxystearic acid, clays, and mixtures thereof. A preferred structurant is described in US Pat. No. 6,855,680, which defines suitable hydroxy-functional crystalline materials in detail. Preferred is hydrogenated castor oil. Some structurants have a linear structural system with various aspect ratios. Another preferred structurant is based on cellulose and can be derived from a number of sources including biomass, wood pulp, citrus fibers, and the like.

The compositions of the present invention may include high melting point fatty compounds. The high melting point fatty compounds useful in the present invention have a melting point of 25°C or higher and are selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof. Such low melting point compounds are not intended to be included in this section. Non-limiting examples of high melting point compounds can be found in the International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and the CTFA Cosmetic Ingredient Handbook, Second Edition, 1992. When present, high melting point fatty compounds are preferably present in an amount of 0.1% to 0.1% by weight of the composition to A concentration of 40%, preferably 1% to 30%, more preferably 1.5% to 16%, 1.5% to 8% is included in the composition.

Cationic polymer. The compositions of the present invention may include cationic polymers. The concentration of cationic polymer in the composition is generally in the range of 0.05% to 3%, in another embodiment in the range of 0.075% to 2.0%, in yet another embodiment in the range of 0.1% to 1.0% . A suitable cationic polymer will have at least 0.5 meq/gm, in another embodiment at least 0.9 meq/gm, in another embodiment at least 1.2 meq/gm, in yet another embodiment at the pH at which the composition is intended to be used A cationic charge density of at least 1.5 meq/gm in an embodiment, but also less than 7 meq/gm in one embodiment, and less than 5 meq/gm in another embodiment, the pH is generally in the range of pH 3 to pH 9, at In one embodiment in the range of pH 4 to pH 8. Here, the "cationic charge density" of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. The average molecular weight of such suitable cationic polymers will typically be 10,000 to 10 million, in one embodiment 50,000 to 5 million, and in another embodiment 100,000 to 3 million.

Suitable cationic polymers for use in the compositions of the present invention contain cationic nitrogen-containing moieties, such as quaternary ammonium or cationic protonated amino moieties. Any anionic counterion can be used in conjunction with the cationic polymer as long as the polymer remains water soluble, soluble in the composition, or soluble in the coacervate of the composition, and as long as the counterion is physically and It is sufficient that it is chemically compatible with the essential components of the composition or does not unduly impair the performance, stability or aesthetics of the product. Non-limiting examples of such counterions include halides (eg, chloride, fluoride, bromide, iodide), sulfate, and methyl sulfate.

Non-limiting examples of such polymers are found in the CTFA Cosmetic Ingredient Dictionary, 3rd Edition, edited by Estrin, Crosley, and Haynes (The Cosmetic, Toiletry, and Fragrance Association), Washington, DC, USA. (1982)).

Other suitable cationic polymers for use in the compositions include polysaccharide polymers, cationic guar gum derivatives, tetravalent nitrogen-containing cellulose ethers, synthetic polymers, etherified celluloses, copolymers of guar gum and starch . When used, the cationic polymers herein are soluble in the composition, or in the complex coacervate phase of the composition formed from the cationic polymer described above and the anionic, amphoteric and/or zwitterionic surfactant components . Complex coacervates of cationic polymers can also be formed with other charged materials in the composition.

Suitable cationic polymers are described in US Patent Nos. 3,962,418, 3,958,581, and US Publication No. 2007/0207109A1.

Nonionic polymer. The compositions of the present invention may include nonionic polymers as modifiers. Polyalkylene glycols with molecular weights greater than 1000 are useful in the present invention. Effective are nonionic polymers having the general formula:

wherein R ⁹⁵ is selected from H, methyl and mixtures thereof.

Conditioners, especially silicones, can be included in the composition. Conditioners useful in the compositions of the present invention generally include water-insoluble, water-dispersible, non-volatile liquids that form emulsified liquid particles. Suitable conditioning agents for use in the compositions are generally characterized as silicones (eg, silicone oils, cationic silicones, silicone rubbers, high refractive silicones, and silicone resins), organic conditioning oils (eg, hydrocarbon oils, polyolefins, and fats) esters) or a combination thereof, or otherwise form liquid dispersed particles in the aqueous surfactant matrix herein. The conditioning agent should be physically and chemically compatible with the essential components of the composition and should not otherwise unduly impair product stability, aesthetics or performance.

The concentration of the conditioning agent in the composition should be sufficient to provide the desired conditioning benefit. The concentration can vary with the conditioning agent, the desired conditioning properties, the average size of the conditioning agent particles, the types and concentrations of other components, and other similar factors.

The concentration of the silicone conditioning agent is generally in the range of about 0.01% to about 10%. Non-limiting examples of suitable silicone conditioning agents and optional suspending agents for silicone are described in US Republished Patent Nos. 34,584; 5,104,646; 5,106,609; 4,152,416; , US Patent Nos. 6,207,782, 7,465,439, 7,041,767, 7,217,777; US Patent Application Nos. 2007/0286837A1, 2005/0048549A1, 2007/0041929A1; UK Patent No. 849,433; Incorporated herein; Silicone Chemistry and Technology, New York: Academic Press (1968); General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54, and SE 76; Silicon Compounds, Petrarch Systems, Inc. ( 1984); and in Encyclopedia of Polymer Science and Engineering, Vol. 15, Second Edition, pp. 204-308, in John Wiley & Sons, Inc. (1989).

聚乙烯亚胺(例如来自巴斯夫公司(BASF)的

)及其锌络合物、银和银化合物中的一个或多个，特别是设计用于缓慢释放Ag+或纳米银分散体的化合物。Organic conditioning oil. The compositions of the present invention may also include, as a conditioning agent, from about 0.05% to about 3% of at least one organic conditioning oil, alone or in combination with other conditioning agents such as silicones (as described herein). Suitable conditioning oils include hydrocarbon oils, polyolefins and fatty esters. Sanitizers The compositions of the present invention may also include components that provide hygienic and/or malodorous benefits, such as zinc ricinoleate, thymol, quaternary ammonium salts such as

Polyethyleneimine (eg from BASF)

) and one or more of its zinc complexes, silver and silver compounds, especially compounds designed for slow release of Ag+ or nanosilver dispersions.

Probiotics. The composition may include probiotics, such as those described in WO2009/043709.

Foam booster. If high foamability is desired, the composition may preferably include a foam booster. Suitable examples are the incorporation of C ₁₀ -C ₁₆ alkanolamides or C ₁₀ -C ₁₄ alkyl sulfates, preferably at a concentration of 1-10%. The _C10 - _C14 monoethanol and diethanolamides illustrate a typical class of foam boosters of this type. It is also advantageous to use such suds boosters with high sudsing co-surfactants such as the amine oxides, betaines and sulfobetaines described above. If desired, water-soluble magnesium and/or calcium salts, such as _MgCl2 , _MgSO4 , _CaCl2 , _CaSO4 , etc., can be added, typically at a concentration of 0.1%-2%, to provide additional foam and enhance oil removal performance.

Foam suppressant. Compounds for reducing or inhibiting foam formation can be incorporated into the compositions of the present invention. Suds suppressors can be especially important in the so-called "high concentration wash process" described in US Patent Nos. 4,489,455 and 4,489,574, and in front loading washing machines. A variety of materials can be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, eg, Kirk-Osmer's Encyclopedia of Chemistry, Third Edition, Vol. 7, pp. 430-447 (John Wiley & Sons, 1979). Examples of suds suppressors include monocarboxylic fatty acids and soluble salts therein, high molecular weight hydrocarbons such as paraffins, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C18-C40 ketones (eg stearyl ketone), N-alkylated aminotriazines, waxy hydrocarbons preferably having melting points below about 100°C, silicone suds suppressors and secondary alcohols. Particularly effective silicone suds suppressors are based on diphenyl-containing silicones.

Silicone suds suppressor. It is usually used in amounts up to 2.0% by weight of the detergent, although higher amounts can be used.

Pearlescent agent. The pearlescent agents described in WO2011/163457 may be incorporated into the compositions of the present invention.

Pearlescent agents can be crystalline or glassy solids, transparent or translucent compounds that reflect and refract light to create a pearlescent effect. Generally, pearlescent agents are crystalline particles that are insoluble in the compositions into which they are incorporated. Preferably, the pearlescent agent has a sheet or spherical shape. The particle size of pearlescent agents is generally below 200 microns, preferably below 100 microns, more preferably below 50 microns. Inorganic pearlescent agents include aluminosilicates and/or borosilicates. Preferred are aluminosilicates and/or borosilicates that have been treated to have a very high refractive index, preferably silica, metal oxides, oxychloride-coated aluminosilicates and/or boron Silicate. A more preferred inorganic pearlescent agent is mica, even more preferred is a titanium dioxide treated mica such as BASF Mearlin Superfine.

The composition may comprise from 0.005% to 3.0% by weight, preferably from 0.01% to 1% by weight of the pearlescent agent, based on the weight of the 100% active pearlescent agent composition. Pearlescent agents can be organic or inorganic. The composition may include organic and/or inorganic pearlescent agents.

Organic Pearlescent Agent:

When the composition includes an organic pearlescent agent, the organic pearlescent agent is included at an active concentration of 0.05% to 2.0% by weight, preferably 0.1% to 1.0% by weight, based on the weight of the composition of 100% active organic pearlescent agent inside. Suitable organic pearlescent agents include mono- and/or diesters of alkylene glycols, such as ethylene glycol distearate.

Inorganic pearlescent agent:

In another embodiment, the composition may also include an inorganic pearlescent agent. When the composition includes an inorganic pearlescent agent, the inorganic pearlescent agent is included at an active concentration of 0.005% to 1.0% by weight, preferably 0.01% to 0.2% by weight, based on the weight of the composition of 100% active inorganic pearlescent agent inside.

suspended particles

In one embodiment, the composition also includes multiple suspended particles. Examples of suitable suspended particles are provided in US Patent No. 7,169,741 and US Patent Publication No. 2005/0203213, the disclosures of which are incorporated herein by reference. These suspended particles may comprise a liquid core or a solid core. Detailed descriptions of these liquid core and solid core particles, as well as preferred particle sizes, particle shapes, particle densities, and particle bursting strengths, are described in US Patent Application Serial No. 12/370,714, the disclosure of which is incorporated herein by reference .

In a preferred embodiment, the particles may be in any discrete and visually distinguishable form of matter, including but not limited to (deformable) pellets, encapsulations, polymeric particles such as plastics, metals such as foils, flakes, glitter), (interference) pigments, minerals (salt, rocks, pebbles, lava, glass/silica particles, talc), plant material (e.g. pits or seeds, plant fibers, pedicles, stems, leaves or roots) , solid and liquid crystal, etc. Different particle shapes are possible, from spherical to flat.

In one embodiment, the suspended particles may be gas bubbles or air bubbles. In this embodiment, the diameter of each bubble can be from about 50 microns to about 2000 microns, and can be from about 0.01% to about 5% by volume of the composition, or from about 0.05% to about 0.05% by volume of the composition 4%, or at a concentration of about 0.1% to about 3% by volume of the composition.

sunscreen

In one embodiment, the composition may also include an opacifier.

As used herein, an "opacifier" is a substance added to a material to opaque the subsequent system. In a preferred embodiment, the sunscreen agent is Acusol, available from Dow Chemicals. Acusol sunscreens are supplied in liquid form at a solid content percentage. Acusol sunscreens are provided with pH in the range of 2.0 to 5.0 and particle size in the range of 0.17 to 0.45um. In a preferred embodiment, Acusol OP 303B and 301 can be used.

In yet another embodiment, the sunscreen may be an inorganic sunscreen. Preferably, the inorganic sunscreen may be _TiO2 , ZnO, talc, _CaCO3 , and combinations thereof. The composite sunscreen-microsphere material is easily formed with a preselected specific gravity, so the material has little tendency to separate.

Hydrotrope: The composition may optionally include a hydrotrope in an effective amount of from about 0% to 15%, or from about 1% to 10%, or from about 3% to about 6%, so that the composition is Compatible in water. Hydrotropes suitable for use in the present invention include anionic hydrotropes, especially sodium, potassium, and ammonium xylene sulfonate; sodium, potassium, and ammonium tosylate; Sodium cumene sulfonate, potassium cumene sulfonate, and ammonium cumene sulfonate, and mixtures thereof, as disclosed in US Pat. No. 3,915,903.

Antioxidant: The composition may optionally contain an antioxidant present in the composition in an amount from about 0.001% to about 2% by weight. Preferably, the antioxidant is present in a concentration of 0.01% to 0.08% by weight. Mixtures of antioxidants can be used.

Antioxidants are substances as described in Kirk-Othmer (Vol. 3, p. 424) and Ullmann's Encyclopedia (Vol. 3, p. 91).

One class of antioxidants used in the present invention are alkylphenols having the general formula:

wherein R is C ₁ -C ₂₂ straight or branched chain alkyl, preferably methyl or branched C ₃ -C ₆ alkyl, C ₁ -C ₆ alkoxy, preferably methoxy; R ₁ is C ₃ - _C6 branched alkyl, preferably tert-butyl; x is 1 or 2. Hindered phenolic compounds are a preferred class of alkylated phenols of this formula. A preferred hindered phenolic compound of this type is 3,5-di-tert-butyl-4-hydroxytoluene (BHT).

In addition, the antioxidant used in the composition may be selected from the group consisting of α-, β-, γ-, δ-tocopherol, somatotropin, 2,2,4-trimethyl-1,2-dihydroquinoline, 2 , 6-di-tert-butylhydroquinone, tert-butylhydroxyanisole, lignosulfonic acid and salts thereof, and mixtures thereof. It should be noted that tropoline (1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline) is sold under the name Raluquin ^™ by the company Raschig ^™ .

Other types of antioxidants that can be used in the compositions are 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox ^™ ) and 1,2-benzothiazoline- 3-keto (Proxel GXL ^™ ).

Another class of antioxidants suitable for use in the composition are benzofuran or benzopyran derivatives of the formula:

wherein R ₁ and R ₂ are each independently alkyl, or R ₁ and R ₂ may together form a C ₅ -C ₆ cyclic hydrocarbyl moiety; B is absent or is CH ₂ ; R ₄ is C ₁ -C ₆ alkyl ; R ₅ is hydrogen or -C(O)R ₃ , wherein R ₃ is hydrogen or C ₁ -C ₁₉ alkyl; R ₆ is C ₁ -C ₆ alkyl; R ₇ is hydrogen or C ₁ -C ₆ alkane radical; X is _-CH2OH or _-CH2A , where A is a nitrogen-containing unit, phenyl or substituted phenyl. Preferred nitrogen-containing A units include amino, pyrrolidino, piperidino, morpholino, piperazino, and mixtures thereof.

Antioxidants such as tocopheryl sorbate, butylated hydroxybenzoic acid and its salts, gallic acid and its alkyl esters, uric acid and its salts, sorbic acid and its salts, and dihydroxyfumaric acid and its salts can also be used. Salt. In one aspect, the most preferred types of antioxidants for use in the composition are 3,5-di-tert-butyl-4-hydroxytoluene (BHT), α-, β-, γ-, δ-tocopherol, 1 , 2-benzothiazolin-3-one (Proxel GXL ^™ ) and mixtures thereof.

The detergent compositions of the present invention may also contain antimicrobial agents. Cationic active ingredients may include, but are not limited to: n-alkyldimethylbenzylammonium chloride, alkyldimethylethylbenzylammonium chloride, dialkyldimethylammonium compounds such as didecyldimethylammonium ammonium chloride, N,N-didecyl-N-methyl-poly(oxyethyl)propionate, dioctyldidecylammonium chloride, and also quaternary ammonium salts such as benzethonium chloride and Quaternary ammonium compounds with inorganic or organic counterions, such as bromine, carbonate or other moieties, including dialkyldimethylammonium carbonate, and antimicrobial amines, such as Chlorhexidine Gluconate, PHMB (poly hexamethylene biguanide), salts of biguanides, substituted biguanide derivatives, organic salts containing quaternary ammonium compounds or inorganic salts containing quaternary ammonium compounds or mixtures thereof.

Package. Any conventional packaging can be used and the packaging can be fully or partially transparent so that the consumer can see the color of the laundry care composition, which color can be provided or produced by the color of the dyes necessary for the present invention. The UV absorbing compound may be included in some or all of the package.

When in liquid form, the laundry care compositions of the present invention may be aqueous (usually above 2 wt% total water or even above 5 or 10 wt% total water up to 90 wt% or up to 80 wt% or 70 wt %) or non-aqueous (usually less than 2 wt % total water content). Typically, the compositions of the present invention will be in the form of aqueous solutions or homogeneous dispersions or suspensions of surfactants, opacifying dyes, and certain optional other ingredients, some of which may usually be in solid form that has been combined with the composition The normally liquid components are combined, such as a non-ionic liquid alcohol ethoxylate, an aqueous liquid carrier and any other normally liquid optional ingredients. The solution, dispersion or suspension will be acceptably phase stable. When in liquid form, the laundry care compositions of the present invention preferably have a viscosity at 20s-1 and 21°C of 1 to 1500 centipoise (1-1500 mPa*s), more preferably 100 to 1000 centipoise Poise (100-1000 mPa*s), and most preferably 200 to 500 centipoise (200-500 mPa*s). Viscosity can be determined by conventional methods. Viscosity can be measured using an AR 550 rheometer from TAInstruments using a steel plate spindle with a diameter of 40 mm and a gap size of 500 μm. A high shear viscosity at 20s-1 and a low shear viscosity at 0.05-1 can be obtained in 3 minutes at 21°C with a logarithmic shear rate sweep from 0.1-1 to 25-1. The preferred rheology described therein can be achieved using internally present detergent ingredients or by using external rheology modifiers. More preferably, the laundry care composition, eg, detergent liquid composition, has a high shear rate viscosity of about 100 cps to 1500 cps, more preferably 100 cps to 1000 cps. Unit dose laundry care compositions, such as detergent liquid compositions, have high shear rate viscosities ranging from 400 cps to 1000 cps. Laundry care compositions such as laundry softening compositions typically have a high shear rate viscosity of 10 cps to 1000, more preferably 10 cps to 800 cps, most preferably 10 cps to 500 cps. The hand dishwashing composition has a high shear rate viscosity of 300 cps to 4000 cps, more preferably 300 cps to 1000 cps.

The liquid compositions, preferably the laundry care compositions herein, can be formed by combining the components thereof in any convenient order and by mixing, eg agitating, the resulting composition of components to form a phase stable liquid laundry care combination thing to prepare. In the method of preparing the composition, a liquid base is formed that contains at least a major proportion, or even substantially all of the liquid components, such as non-ionic surfactants, non-surface-active liquid carriers and other optional liquid components, and the liquid components are thoroughly mixed by shearing the liquid composition. For example, a mechanical stirrer can be used for rapid stirring. While maintaining shear agitation, substantially all of any anionic surfactant and solid form ingredients may be added. Stirring of the mixture is continued and, if necessary, increased at this point to form a solution or uniform dispersion of insoluble solid phase particles within the liquid phase. After some or all of the solid form material is added to the stirred mixture, particles of any enzymatic material to be included, eg, enzyme particles, are incorporated. As a variation of the above composition preparation process, one or more solid components can be added to the agitated mixture as a solution or slurry of particles premixed with a small amount of one or more liquid components . After all composition components have been added, the mixture is continued to be stirred for a period of time to form a composition with the necessary viscosity and phase stability characteristics. Typically, this requires stirring for about 30 to 60 minutes.

The leuco colorants of the present invention have been found to be suitable for use in liquid laundry care compositions having a wide pH range. For example, the leuco colorants of the present invention have been found to be suitable for use in liquid laundry care compositions having a pH of greater than or equal to 10. Furthermore, the leuco colorants of the present invention have been found to be suitable for use in liquid laundry care compositions having a pH of less than 10. Thus, leuco colorants are stable in laundry care compositions at pH values of 10 or greater and 10 or less.

bag. In a preferred embodiment of the invention, the composition is provided in the form of a unitized dose, which is in the form of a tablet, or preferably in a water-soluble film called a pouch or sachet in liquid/solid (optionally granular)/gel/paste form. The composition may be enclosed in a single-compartment bag or a multi-compartment bag. Multi-compartment bags are described in more detail in EP-A-2133410. When the composition is present in a multi-compartment bag, the composition of the present invention may be present in one or two or more compartments and thus the dye may be present in one or more compartments, optionally in all compartments. Non-opaque dyes or pigments or other aesthetic materials can also be used in one or more of the compartments. In one embodiment, the composition is present in a single compartment of a multi-compartment bag.

Preferred membrane materials are polymeric materials. Film materials can be obtained, for example, by casting, blow molding, extrusion or blow extrusion of polymeric materials, as known in the art. Preferred polymers, copolymers or derivatives thereof suitable for use as bag materials are selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polyoxyalkylene, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, Polyvinyl acetates, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamides, maleic/acrylic acid copolymers, polysaccharides including starch and gelatin, natural gums such as xanthan and carrageenan. More preferred polymers are selected from the group consisting of polyacrylates and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose methacrylate, maltodextrin, polymethacrylate, and most preferably selected from polyvinyl alcohol, polyvinyl alcohol copolymers, and hydroxypropyl methylcellulose (HPMC), and combinations thereof. Preferably, the content of polymer, eg PVA polymer, in the bag material is at least 60%. The polymer may have any weight average molecular weight, preferably about 1000 to 1,000,000, more preferably about 10,000 to 300,000, still more preferably about 20,000 to 150,000. Mixtures of polymers can also be used as bag materials. Depending on the application and desired requirements of the compartment or bag, it may be beneficial to control the mechanical and/or dissolution properties of the compartment or bag. Suitable mixtures include, for example, mixtures in which one polymer is more water soluble than the other polymer, and/or one polymer has a higher mechanical strength than the other polymer. Also suitable are mixtures of polymers having different weight average molecular weights, such as PVA or copolymers thereof having a weight average molecular weight of about 10,000 to 40,000, preferably about 20,000, and a weight average molecular weight of about 100,000 to 300,000, preferably about 150,000 of PVA or its copolymers. Also suitable herein are polymer blend compositions, including, for example, hydrolytically degradable and water-soluble polymer blends, such as polylactide and polyvinyl alcohol, by combining polylactide and polyvinyl alcohol Instead, it typically contains about 1-35% by weight of polylactide and about 65% to 99% by weight of polyvinyl alcohol. Preferred for use herein are polymers that are hydrolyzed from about 60% to about 98%, preferably from about 80% to about 90% hydrolyzed, to improve the dissolution characteristics of the material.

Naturally, different membrane materials and/or membranes of different thicknesses may be employed in the manufacture of the compartments of the present invention. The benefit of choosing different membranes is that the resulting compartments can exhibit different solubility or release characteristics.

The most preferred membrane materials are the PVA membranes known under MonoSol trade numbers M8630, M8900, H8779, the PVA membranes described in US Pat. PVA film.

The film materials herein may also include one or more additive components. For example, it may be beneficial to add plasticizers such as glycerol, ethylene glycol, diethylene glycol, propylene glycol, sorbitol, and mixtures thereof. Other additives include functional detergent additives to be delivered to the wash water, such as organic polymeric dispersants and the like.

solid form. As mentioned above, the laundry care composition may be in solid form. Suitable solid forms include tablets and granular forms such as granules, flakes or sheets. Various techniques for forming such solid form detergent compositions are well known in the art and can be used herein. In one aspect, such as when the composition is a granular particle, the leuco colorant is provided in particulate form, optionally including additional but not all components of the laundry detergent composition. The colorant particles are combined with one or more additional particles containing the remaining components of the laundry detergent composition. In addition, colorants, optionally including other, but not all, components of the laundry care composition can be provided in encapsulated form, and the opacifying dye encapsulates are combined with granules containing a substantial balance of the components of the laundry care composition.

Instructions. The compositions of the present invention prepared as described above can be used to form aqueous wash/treatment solutions for use in the laundering/treatment of fabrics. Typically, such as in conventional automatic fabric washing machines, an effective amount of such compositions is added to water to form the aqueous wash solution. The aqueous wash solution thus formed is then contacted with the fabric to be washed/treated, usually with agitation. An effective amount of the liquid detergent compositions herein added to water to form an aqueous wash solution may include sufficient to form about 500 ppm to 7,000 ppm of the composition in an aqueous wash solution, or about 1,000 to 3,000 ppm of the wash care compositions herein will provide in the wash in aqueous solution.

Typically, the wash liquor is prepared by mixing the wash care composition with the wash water so that the concentration of the wash care composition in the wash liquor is from 0 g/l to 5 g/l, or 1 g/l to 4.5 g/l, or to 4.0 g /l, or to 3.5 g/l, or to 3.0 g/l, or to 2.5 g/l, or even to 2.0 g/l, or even to 1.5 g/l. The method of laundering fabrics or textiles can be carried out in a top-loading or front-loading automatic washing machine, or can be used in hand-wash laundry applications. In these applications, the resulting wash liquor and laundry detergent compositions are at concentrations in the wash liquor that are the concentrations of the main wash cycle. Water input in any optional rinse steps is not included when determining the volume of wash solution.

The wash liquor may comprise 40 liters or less of water, or 30 liters or less of water, or 20 liters or less of water, or 10 liters or less of water, or 8 liters or less of water, or even 6 liters or less of water. The wash solution can include more than 0 to 15 liters, or 2 liters to 12 liters, or even 8 liters of water. Typically 0.01 kg to 2 kg of fabrics are dosed into the wash liquor per liter of wash liquor. Typically from 0.01 kg, or 0.05 kg, or 0.07 kg, or 0.10 kg, or 0.15 kg, or 0.20 kg, or 0.25 kg of fabric per liter of wash liquor is dosed to the wash liquor. Optionally, make 50g or less, or 45g or less, or 40g or less, or 35g or less, or 30g or less, or 25g or less, or 20g or less, or even 15g or Less, or even 10 g or less of the composition is contacted with water to form a wash liquor. The compositions are typically used at a concentration of from about 500 ppm to about 15,000 ppm in solution. When the wash solvent is water, the water temperature is typically in the range of about 5°C to about 90°C, and when the location includes fabric, the water to fabric ratio is typically about 1:1 to about 30:1. Typically, the pH of the wash liquor comprising the laundry care compositions of the present invention is from 3 to 11.5.

In one aspect, a method is disclosed comprising the steps of: optionally washing and/or rinsing the surface or fabric; contacting the surface or fabric with any of the compositions disclosed in this specification; then optionally washing and/or rinsing the fabric. /or rinsing the surface or fabric, and optional drying step.

Drying of the surface or fabric can be accomplished by any of the usual methods employed in domestic or industrial settings. The fabric can include any fabric that can be laundered under normal consumer or institutional use conditions, and the present invention is applicable to cellulosic substrates, and in some aspects synthetic fabrics, such as polyester and nylon, and to Process mixed fabrics and/or fibers, including synthetic and cellulosic fabrics and/or fibers. Examples of synthetic fabrics are polyester, nylon, which may be present in mixtures of cellulosic fibers, eg, polycotton fabrics. The pH of the solution is typically 7 to 11, more typically 8 to 10.5. The composition is typically used at a concentration of 500 ppm to 5,000 ppm in solution. The water temperature is usually about 5°C to about 90°C. The ratio of water to fabric is typically about 1:1 to about 30:1.

Accordingly, in a third embodiment, the present invention provides a method of treating textiles. The method preferably includes the steps of: (i) treating textiles with an aqueous solution containing the leuco composition described herein; (ii) optionally rinsing the textiles; and (iii) drying the textiles. In one aspect, the present invention provides a method of treating textiles, the method comprising the steps of: (i) treating textiles with an aqueous solution comprising a leuco composition as described herein, the aqueous solution comprising 10 ppb to 5000 ppm of at least one a leuco compound and 0.0 g/L to 3 g/L of surfactant; (ii) optionally rinsing; and (iii) drying the textile. The leuco composition used in this method can be any of the leuco compositions described herein. Furthermore, the aqueous solutions used in the method can be produced by adding the leuco composition directly to the aqueous medium or by adding a laundry care composition containing the leuco composition to the aqueous medium.

testing method

Fabric swatches used in the test methods herein were obtained from Testfabrics, Inc., West Pittston, PA; the fabric swatches were 100% cotton, 403 (cut 2 inches by 2 inches) and/or 464 (cut 2 inches by 2 inches) 4 inches by 6 inches), and a non-whitened multifiber fabric, specifically, a 41 pattern (5 cm by 10 cm).

7000A(GretagMacbeth，美国纽约州New Windsor；D65灯，不含紫外线)，或者(4)Color i7分光光度计(X-rite,Inc.，美国密歇根州Rapids；D65灯，不含紫外线)。All reflectance spectral and color measurements of dry textile swatches—including L*, a*, b*, K/S, and Whiteness Index (WICIE) values—are measured using one of the following four spectrophotometers: (1 ) Konica-Minolta 3610d reflectance spectrophotometer (Konica Minolta Sensing Americas, Inc., Ramsey, NJ, USA; D65 illumination, 10° observer, excluding UV), (2) LabScan XE reflectance spectrophotometer (HunterLabs, Virginia, USA) Reston, WA; D65 Illumination, 10° Observer, UV Free), (3)

7000A (GretagMacbeth, New Windsor, NY, USA; D65 lamp, UV-free), or (4) Color i7 spectrophotometer (X-rite, Inc., Rapids, MI, USA; D65 lamp, UV-free).

When irradiating fabrics, unless otherwise stated, the specified dried fabrics ^were exposed to a simulated irradiance of 0.77 W/m at 420 nm in an Atlas Xenon Fade-Ometer Ci3000+ (Atlas Material Testing Technology, Mount Prospect, IL, USA) In sunlight, the Atlas Xenon Fade-Ometer Ci3000+ is fitted with an S-type borosilicate internal filter (part no. 20277300) and an external filter (part no. 20279600), set at a maximum cabinet temperature of 37°C and a maximum blackboard temperature At 57°C (BPT blackboard geometry) and 35% RH (relative humidity). Irradiation is continuous for the stated duration unless otherwise stated.

I. Method for Determining Leuco Conjugate Efficiency in Washing Solutions

The cotton swatches (Form 464) were stripped by washing twice at 49°C with zero brightener heavy duty liquid laundry detergent (1.55g/L in water) prior to use . Concentrated stock solutions of each leuco composition to be tested are prepared in a solvent selected from ethanol or 50:50 ethanol:water, preferably ethanol.

All L*, a*, b* and Whiteness Index (WI CIE) values of cotton fabrics were measured on dry swatches using a Konica-Minolta 3610d reflection spectrophotometer.

A base wash was prepared by dissolving AATCC Heavy Duty Liquid Laundry Detergent (5.23 g/1.0 L) with zero brightener in deionized water. Four stripped cotton swatches were weighed together and placed in a 250 mL Erlenmeyer flask along with two 10 mm glass balls. A total of three such flasks are prepared for each wash solution to be tested. The leucoconjugate stock solution was dosed to the base wash to obtain a wash with the desired 2.00 x ^10-6 equiv/L leucoconjugate wash concentration.

An aliquot of the wash solution sufficient to provide a liquid:fabric ratio (weight ratio, w/w) of 10.0:1.0 was placed into each of three 250 mL Erlenmeyer flasks. 1000 gpg hardness stock solution was dosed to each flask to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg).

The flask was placed on a Model 75 wrist action shaker (Burrell Scientific, Inc., Pittsburgh, PA, USA) and stirred at maximum setting for 12 minutes, then the wash was removed by suction to match the wash used. A volume equivalent to the amount of liquid was added to rinse water (0 gpg). 1000 gpg hardness stock solution was dosed to each flask to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg), followed by stirring for an additional 4 minutes. Rinse was removed by suction, then the cotton swatches were spin-dried (Mini Countertop Spin Dryer, The Laundry Alternative Inc., Nashua, NH, USA) for 1 minute and then placed in food set at 135°F In a dehydrator, dry in the dark for 2 hours. After this drying procedure, the samples can be stored in the dark or exposed to light for various times before measuring the fabric properties.

Because the habits of consumers around the world vary significantly, the method used must be able to measure the benefits of leuco compounds in a variety of situations. One such condition is exposure to light after drying. Some leuco compounds do not exhibit as great a benefit under dark storage as they do under light storage, so each leuco compound must be tested under both sets of conditions to determine the best benefit. Thus, Method 1 involves exposing the dried fabric to simulated sunlight for various increments of time, then measuring and setting the LCE value to the maximum value obtained from the set of exposure times described below.

A. Dark conditions after drying

After drying, the fabrics were stored in the dark at room temperature between measurement time points. Cotton fabrics were measured for L*, a*, b* and Whiteness Index (WI CIE) values at times t=0, 6, 24 and 48 hours after the two hour drying time. The values of 12 swatches (three flasks, 4 swatches each) generated for each leuco colorant were averaged to derive L*, a*, b* and WI for each time point t Sample values for CIE.

To obtain the L*, a*, b* and Whiteness Index (WI CIE) values for the control treatment, repeat the above procedure except for the following: (1) AATCC Heavy Duty Liquid Laundry with zero brightener in deionized water Detergent (5.23g/1.0L) to prepare a control base wash, (2) the values measured after the drying period for 12 swatches generated against the control were averaged to derive L*, a*, b* and WI CIE, and the control value at t=0 was also used as the control value at t=6, 24 and 48 hours.

Based on the data collected at each time point t, the leuco Colorant Efficiency (LCE) of the leuco colorant in the laundry care formulation was calculated using the following equation:

LCE _t =DE*=((L* _c -L* _s ) ² +(a* _c -a* _s ) ² +(b* _c -b* _s ) ² ) ^1/2

where the subscripts c and s refer, respectively, to the control (i.e. fabrics washed with zero brightener AATCC heavy duty liquid laundry detergent) and the sample (i.e. fabrics washed with leuco colorant-containing laundry care formulations), where the values used to calculate LCE _t were those at the corresponding time point t (0, 6, 24 or 48 hours).

The WI CIE values for 12 swatches generated for each wash solution (three flasks, 4 swatches per flask) were averaged and the change in whiteness index over wash was calculated using the following equation:

ΔWI = WI CIE (after washing) – WI CIE (before washing)

The value by which the AATCC HDL (ΔWI _control ) of the laundry care formulation (ΔWI _sample ) and zero brightener would be separated. The change in whiteness between the two formulations is given by:

δΔWI＝ΔWI _sample –ΔWI _control

B. Light conditions after drying

After drying, the indicated cotton fabrics were exposed to simulated sunlight for 15 minutes, 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 120 minutes and 240 minutes. L*, a*, b* and Whiteness Index (WI CIE) values of cotton fabrics were measured on the samples after each exposure period. The LCE and ΔWI values for each exposure time point were calculated as described in Method I.A. above, and the LCE and ΔWI values for the sample and control laundry care formulations were set to the maximum value obtained from the set of exposure times listed .

II. Method for Determining Relative Hue Angle (Relative to AATCC Control)

The relative hue angle imparted by the leuco colorant to cotton fabrics treated according to Method I above was determined in the following manner.

a) Average the a* and b* values for 12 swatches in each solution and determine Δa* and Δb* using the following equations:

Δa*=a* _s -a* _c and Δb*=b* _s -b* _c

where subscripts c and s refer to fabrics washed in zero brightener AATCC heavy duty liquid laundry detergent (control) and fabrics washed in laundry care formulations containing leuco colorants (sample), respectively.

b) If the absolute values of Δa* and Δb* are both < 0.25, the relative hue angle (RHA) is not calculated. If the absolute value of Δa* or Δb* is ≥ 0.25, use one of the following equations to determine the RHA:

RHA=ATAN2(Δa*,Δb*) for Δb*≥0

RHA=360+ATAN2(Δa*,Δb*) for Δb*<0

The relative hue angle can be calculated for each time point where data was collected in the evaluation in the dark after drying or the evaluation in the light after drying. Any of these points in time can be used to satisfy the claims.

III. Method for determining surface tension values of leuco colorants and their oxidized forms.

过滤器，将等分试样过滤到20mL闪烁管中。使用VWR LabMax移液器移液以将45.0微升的过滤后溶液输送到96孔板的八个单独的孔中的每个孔中。用Kibron Delta 8张力计在约22.0℃下测试该溶液，并以表面张力值(单位mN/m)报告8个测量的重复的平均值。The material to be tested is a leuco colorant according to the invention, or a dye representing a second colored state of a leuco colorant (eg triarylmethane dye). A total of 250-255 mg of material to be tested was weighed into a 4 oz glass jar and 50.0 mL of deionized water (Barnstead B-Pure System, about 17.27 ohm) was added along with a magnetic stir bar. The glass jar was capped, placed on a magnetic stir plate, and the mixture was stirred at 22.0°C for 1 hour. After this time stirring was stopped and the mixture was left as it was for 1 hour. At the end of this time, 10.0 mL of the solution was drawn into a syringe, which was then fitted with fiberglass

filter, filter aliquots into 20 mL scintillation vials. A VWR LabMax pipette was used to transfer 45.0 microliters of the filtered solution into each of eight separate wells of a 96-well plate. The solution was tested with a Kibron Delta 8 tensiometer at about 22.0°C and the average of 8 replicates of the measurements reported as surface tension values (in mN/m).

Example 1

Determining the bias of the leuco colorant to increase the whiteness of aged garments relative to the whiteness of clean new garments.

Testing was conducted using leuco Colorants 1 and 2 to determine the extent to which the leuco compounds provide improved whiteness to consumer source aged cotton fabrics and to clean, stripped new cotton fabrics. The structures of the leuco colorants tested are shown below.

Leuco Colorant 1 (a+b=0) and Leuco Colorant 2 (a+b=2.8; sum of a+b=5.6)

Tests were performed on stripped cotton fabrics according to Method I.A. found herein, with Formula 403 in place of Formula 464. The test procedure was then re-performed as described, substituting the stripped cotton with swatches cut from consumer source aged white t-shirt fabric (St. Vincent DePaul 4" x 6" T-shirt Swatches, heavily soiled; available from J&R Coordinating Services, Cincinnati, OH, USA), wherein the T-shirt swatches had the L*, a*, b* and WI CIE values before laundering as shown in Table 1 below. When testing consumer-sourced aged white T-shirts, only two replicates were placed in each wash flask.

Table 1. Average values for consumer-sourced aged cotton T-shirts before laundering.

For stripped cotton fabrics washed in the compositions according to Method I.A. and aged white T-shirt fabrics of consumer origin, the change in Whiteness Index (ΔWI) was calculated according to the equation provided in the method using after drying WI CIE values measured at 2, 24 and 48 hours were used for the calculations in each case.

By comparing the change in whiteness index of the same fabrics washed in two detergent formulations, namely the control (zero leuco colorant) and the sample (containing leuco colorant), it was concluded that due to the presence of change in whiteness due to leuco colorants; and this change in whiteness is calculated by the equation provided in Methods. The results of the wash tests are shown in Table 2 below.

Table 2. Bias ratio of whitening of aged consumer cotton garments relative to clean cotton.

^a 100% cotton, Type 403, Test Fabrics, Inc., stripped.

^b 100% cotton, sourced from consumer white T-shirts.

The data in Table 2 show that leuco colorants comprising moieties with EO and PO oxyalkylene groups have a bias towards increasing the brightness of aged consumer cotton fabrics relative to increasing the brightness of new clean cotton fabrics, which consistently This bias is consistently greater than that obtained by leuco colorants comprising moieties having only EO alkylene oxide units. This means that the use of such a leuco colorant (eg 2) will provide the same whiteness benefit to aged cotton fabrics as a leuco compound with only EO oxyalkylene groups (eg 1) without damaging the new cotton Color integrity of clothing. Thus, the inventive leuco colorants of the present invention provide consumers with a distinct advantage in depositing efficiently where they are needed (aged cotton fabrics prone to yellowing) while avoiding deposition where color adjustment is neither needed nor desired on new cleaning fabrics.

Example 2

Leuco Colorant J (average a+b ≈ 2.5; sum of all a+b ≈ 5.0)

Various cotton fabrics (Testfabrics, Inc., West Pittston, PA; 100% cotton, cut to 4 inches by 6 inches) were divided into two equivalent groups and tested as-is, except that: Two additional sets of #403 style sheets (CW120 cotton, cut 4 inches by 4 inches; different lot numbers from the first set) were stripped as described below and added to the test set. One group was washed with a heavy duty liquid detergent with zero leuco colorant (Formulation A) and another group was washed with the same detergent with leuco colorant J (Formulation B). Each wash was run for 12 minutes at a 12:1 liquid-to-fabric ratio using city water (approximately 6 gpg, 3:1 Ca:Mg) and a 5,300 ppm heavy duty liquid detergent formulation, the composition of which is listed in the table below 3 in. Rinse for four minutes using city water at a 12:1 liquid to fabric ratio. The fabric was then air-dried at room temperature in the dark for 48 hours.

Table 3. Heavy Duty Liquid Detergent Formulations A and B

L*, a* of cotton fabrics were measured on dry swatches using a CM3610d spectrophotometer (Konica Minolta, Ramsey, NJ, USA; D65 illumination, 10° observer, excluding UV) before laundering and 48 hours after laundering , b* and Whiteness Index (WI CIE) values. The WI CIE values of replicate swatches generated for each laundry care formulation were averaged and the change in whiteness index in the wash was calculated using the following equation:

ΔWI = WI CIE (after washing) – WI CIE (before washing)

The change in whiteness due to the addition of leuco colorant J to the wash liquor is obtained by comparing the change in whiteness index of the same Style # fabrics washed in both detergent formulations A and B; and is calculated by the following equation This whiteness change is derived:

δΔWI _CIE = ΔWI (detergent B) – ΔWI (detergent A)

The results for the fabrics are presented in the table below, numerically based on the values of delta WI _CIE obtained. The tested fabric IDs and their results are listed in Table 4 below.

Table 4. Delta WI _CIE values obtained for various standard cotton fabrics.

Note that the change in whiteness values can vary widely between washes in the two detergents, depending on the specific type of cotton fabric used in the test. This is true even for cottons of the same style #, one of which has been washed twice at 49°C with zero brightener AATCC Heavy Duty Liquid Laundry Detergent (1.55g/L in water) prior to use to strip (resulting in a δΔWI CIE value of 1.93), the other was unpeeled (resulting in a δΔWI CIE value of 0.72). This indicates that a given detergent formulation used by a consumer will encounter textiles that represent a wide range of possibilities, and that the mode of action of the formulation on some textiles will often be significantly different than on others. These differences can be found by routine experimentation, as shown in the data above.

Example 3

The fully oxidized forms of Leuco Colorants 1 and J from Examples 1 and 2, respectively, were deposited on a 403-style cotton swatch through a wash cycle. As noted above, the oxidized form of leuco Colorant J was also deposited through the wash cycle on the above consumer source aged white T-shirt fabric. Fabric samples were tested for photofading by exposing them to simulated sunlight with an irradiance of 0.77 W/m at 420 nm in an Atlas Xenon Fade ^- Ometer Ci3000+ (AtlasMaterial Testing Technology, Mount Prospect, IL, USA). degree; wherein the AtlasXenon Fade-Ometer Ci3000+ is fitted with an S-type borosilicate internal filter (part no. 20277300) and an external filter (part no. 20279600), set at a maximum cabinet temperature of 37°C and a maximum blackboard temperature of 57°C °C (BPT blackboard geometry) and 35% RH (relative humidity). Type 403 fabrics were exposed continuously for 30 minutes and 120 minutes; aged white T-shirts of consumer origin were exposed continuously for 120 minutes. After 30 and 120 minutes of irradiation, the fading of leuco colorant J was less than that of leuco colorant 1. After 120 minutes, the fading of Leuco Colorant J was similar on clean fabrics and aged white T-shirts of consumer origin.

Example 4

This example demonstrates the preparation of compounds according to the invention having the following structure

12.45 grams of 4-acetamidobenzaldehyde and aniline-2,4 (aniline alkoxylated with an average of 2 EO and 4 PO) were added to a three-way chamber equipped with a heating mantle, stirrer, condenser and nitrogen inlet. necked round bottom flask. Then, 2.71 grams of urea was dissolved in 18 grams of water, and this solution was added to the reaction. After mixing, 23.74 g of concentrated HCl (37%) was slowly added to the reaction mixture while maintaining the temperature below 90°C. The reaction mixture was stirred at 90°C under nitrogen for 6 hours. After the reaction was complete, the contents of the flask were added to excess sodium bicarbonate solution (30 g in 600 mL of water). The product was extracted from the resulting mixture using ethyl acetate and washed with deionized water. Ethyl acetate was removed using a rotary evaporator and the resulting product was dried in a vacuum oven.

Formulation Examples

The following are illustrative examples of cleaning compositions according to the present disclosure, and are not intended to be limiting.

Examples 3-9: Heavy Duty Liquid Laundry Detergent Compositions.

Based on the total weight of the washing and/or treatment composition. Enzyme levels are reported as feedstocks.

Examples 10 to 20: Unit Dose Compositions.

These examples provide various formulations for unit dose laundry detergents. Compositions 8 to 12 contain a single unit dose compartment. The film used to encapsulate the composition is a polyvinyl alcohol based film.

Based on the total weight of the washing and/or treatment composition. Enzyme levels are reported as feedstocks.

In the following examples, the unit dose has three compartments, but similar compositions can be made with two, four or five compartments. The membrane used to encapsulate the compartments is polyvinyl alcohol.

Enzyme levels are reported as raw materials based on the total weight of the wash and/or treatment composition.

AE1.8S is C _12-15 alkyl ethoxy (1.8) sulfate

AE3S is C _12-15 alkyl ethoxy (3) sulfate

AE7 is a C _12-13 alcohol ethoxylate with an average degree of ethoxylation of 7

AE8 is a C _12-13 alcohol ethoxylate with an average degree of ethoxylation of 8

AE9 is a C _12-13 alcohol ethoxylate with an average degree of ethoxylation of 9

15mg活性物质/g，其由Novozymes提供Amylase 1 is

15mg active substance/g provided by Novozymes

29mg活性物质/g，其由Novozymes提供Amylase 2 is

29 mg active substance/g provided by Novozymes

20mg活性物质/g，其由Novozymes提供Xyloglucanase is

20mg active substance/g provided by Novozymes

Chelating agent 1 is diethylenetriaminepentaacetic acid

Chelating agent 2 is 1-hydroxyethane 1,1-diphosphonic acid

Dispersin B is a glycoside hydrolase, reported as 1000 mg active substance/g

)或是DTI or poly(4-vinylpyridine-1-oxide) (eg Chromabond

) or

)。Poly(1-vinylpyrrolidone-co-1-vinylimidazole) (eg Sokalan

).

O.IN(M1)、

P(M2)、Dye Control Agents Dye control agents according to the present invention, such as

O.IN(M1),

P(M2),

PM(M3)或

HF(M4)

PM(M3) or

HF(M4)

HSAS is mid-branched as disclosed in US 6,020,303 and US 6,060,443

Alkyl sulfate

LAS is a linear alkylbenzene sulfonate with an average aliphatic carbon chain length of _C9 - _C15 (HLAS is an acid

form).

Leuco Colorants Any suitable leuco colorants or mixtures thereof according to the present disclosure.

18mg活性物质/g，其由Novozymes提供Lipase is

18 mg active substance/g provided by Novozymes

V200 是噻吩偶氮染料，其由Milliken提供

V200 is a thiophene azo dye supplied by Milliken

25mg活性物质/g，其由Novozymes提供Mannanase is

25mg active substance/g provided by Novozymes

Nuclease is phosphodiesterase SEQ ID NO 1, reported as 1000 mg active substance/g

Optical Brightener 1 is 4,4'-bis{[4-anilino-6-morpholino- s -triazin-2-yl]-amino}-2,2'-di

disodium styrene disulfonate

Optical brightener 2 is 4,4'-bis-(2-sulfostyryl) biphenyl disodium (sodium salt)

Optical Brightener 3 is Optiblanc from 3V Sigma

The fragrance encapsulates are core-shell melamine formaldehyde fragrance microcapsules.

The polishing enzyme is p-nitrobenzyl esterase, which is reported as 1000 mg active substance/g

Polymer 1 is bis(( _C2H5O ) _{( C2H4O} ) _n )( _CH3 ) _-N ⁺ _-CxH2x -N ⁺ -( _{CH3 )} -bis( _{( C2H5} O)(C ₂ H ₄ O)

n) or its sulfated or sulfonated variants, where n=20 to 30 and x=3 to 8

Polymer 2 is ethoxylated (EO ₁₅ ) tetraethylenepentamine

Polymer 3 is an ethoxylated polyethyleneimine

Polymer 4 is ethoxylated hexamethylenediamine

Polymer 5 was Acusol 305 supplied by Rohm & Haas

Polymer 6 is a polyethylene glycol polymer grafted with vinyl acetate side chains, supplied by BASF.

40.6mg活性物质/g，其由DuPont提供Protease is Purafect

40.6 mg active/g provided by DuPont

The structurant is hydrogenated castor oil

Dimensions and numerical values disclosed herein are not to be construed as strictly limited to the exact numerical values recited. Instead, unless stated otherwise, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40mm" is intended to mean "about 40mm".

Unless expressly excluded or otherwise limited, the entire contents of each document cited herein (including any cross-referenced or related patent or application and any patent application or patent from which this application claims priority or benefit) are This is incorporated herein by reference. Citation of any document does not imply an admission that it is prior art with respect to any invention disclosed or claimed herein, or that it teaches, alone or in any combination with one or more of any other reference, Any such invention is implied or disclosed. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall control.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is intended to cover in the appended claims all such changes and modifications as are within the scope of this invention.

Claims (17)

1. A leuco composition comprising at least one leuco compound comprising a leuco moiety and an alkylene oxide moiety covalently bonded to the leuco moiety, wherein the alkylene oxide moiety Contains at least one ethylene oxide group and at least one propylene oxide group. 2. leuco composition according to claim 1, wherein said leuco moiety is selected from diarylmethane leuco moiety, triarylmethane leuco moiety, oxazine moiety, thiazine moiety, hydroquinone moiety and aromatic moiety. aminophenol moiety. 3. The leuco composition of claim 2, wherein the leuco moiety is a triarylmethane leuco moiety. 4. The leuco composition of any one of claims 1-3, wherein the alkylene oxide moiety comprises 1 to about 20 ethylene oxide groups and 1 to about 20 propylene oxide groups group. 5. The leuco composition of any one of claims 1-4, wherein the alkylene oxide moiety is covalently bonded to the leuco moiety through a nitrogen atom, the nitrogen atom and the alkylene The radical oxygen moieties together have the structure—NR ¹ (C ₂ H ₄ O) _n (C ₃ H ₆ O) _q H, wherein n and q are independently selected from integers from 1 to 5, and R ¹ is selected from hydrogen, alkyl , substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl and alkylene oxide moieties. 6. The leuco composition of any one of claims 1-5, wherein the leuco compound comprises two alkylene oxide moieties, each alkylene oxide moiety covalently bonded to the leuco through a nitrogen atom. the leuco moiety, the nitrogen atom and the alkylene oxide moiety together have the structure

wherein n, q, r, and s are independently selected from integers from 0 to 5, the sum of n and r is 2 to 10, and the sum of q and s is 2 to 10. 7. The leuco composition of claim 6, wherein the sum of n and r is 2 to 5, and the sum of q and s is 2 to 5. 8. The leuco composition according to any one of claims 1-7, wherein the leuco compound has the structure of formula (CI)

wherein the ratio between formula (CI) and its oxidized form is at least 1 :3; wherein each individual R _o , R _m and R _p group on each of rings A, B and C is independently selected from hydrogen, deuterium, and R ⁵ ; wherein each R ⁵ is independently selected from halogen, nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, —(CH ₂ ) _n ─O─R ¹ , ─(CH ₂ ) _n ─NR ¹ R ² , ─C(O)R ¹ , ─C(O)OR ¹ , ─C(O)O ^- , ─C(O) NR ¹ R ² , ─OC(O)R ¹ , ─OC(O)OR ¹ , ─OC(O)NR ¹ R ² , ─S(O) ₂ R ¹ , ─S(O) ₂ OR ¹ , ─ S(O) ₂ O ^- , ─S(O) ₂ NR ¹ R ² , ─NR ¹ C(O)R ² , ─NR ¹ C(O)OR ² , ─NR ¹ C(O)SR ² , ─ NR ¹ C(O)NR ² R ³ , ─P(O) ₂ R ¹ , ─P(O)(OR ¹ ) ₂ , ─P(O)(OR ¹ )O ^- and ─P(O)(O ^- ) ₂ ; wherein subscript n is an integer from 0 to 4, preferably 0 to 1, most preferably 0; wherein G is independently selected from hydrogen, deuterium, _C1 - _C16 alkoxides, phenates, bisphenolates, nitrites, nitriles, alkylamines, imidazoles, arylamines, polyoxyalkylenes, halides, alkyls Sulfides, aryl sulfides and phosphine oxides; wherein R ¹ , R ² and R ³ are independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and R ⁴ ; R ⁴ is the Alkyloxy moiety; Wherein, any charge present in the compound is balanced with an appropriate independently selected internal or external counterion. 9. The leuco composition of claim 8, wherein G is hydrogen. 10. The leuco composition according to any one of claims 1-9, wherein the leuco composition also comprises a composition selected from the group consisting of water, ethylene glycol, propylene glycol, glycerol, poly(ethylene glycol), poly(ethylene glycol) propylene glycol), copolymers of ethylene oxide and propylene oxide, and solvents in their mixtures. 11. The leuco composition of any one of claims 1-10, wherein the leuco compound is present in the composition in an amount of about 10% by weight or greater. 12. The leuco composition of any one of claims 1-11, wherein the leuco composition further comprises an antioxidant compound. 13. The leuco composition of claim 12, wherein the antioxidant compound is selected from the group consisting of hindered phenols, diarylamines, benzofurans, and mixtures thereof. 14. The leuco composition according to claim 13, wherein the leuco composition comprises from about 0.01% to about 20% by weight of hindered phenol, preferably BHT. 15. A leuco composition obtained by (i) providing one molar equivalent of an aromatic aldehyde, (ii) providing about two molar equivalents of an aryl coupling agent or a mixture of aryl coupling agents, wherein at least An aryl coupling agent comprising covalently bound oxyalkylene or polyoxyalkylene moieties, wherein the oxyalkylene or polyoxyalkylene moieties comprise at least one ethylene oxide group and at least one propylene oxide group, (iii ) combining the aromatic aldehyde and one or more aryl coupling agents in a suitable reaction vessel, (iv) adding 0.01 to 0.5 equivalents of urea, (v) adding technical grade hydrochloric acid to achieve about 0 to 3 pH between, (vi) heating the mixture between 60°C and 120°C for 2 hours to 12 hours, (vii) adjusting the pH to at least about 7, and (viii) forming the At least a portion of the salt is isolated from the liquid product; wherein the leuco composition comprises at least one leuco compound comprising a leuco moiety and an alkylene oxide moiety covalently bonded to the leuco moiety , wherein the alkylene oxide moiety comprises at least one ethylene oxide group and at least one propylene oxide group. 16. The leuco composition of claim 15, wherein the leuco compound has formula (CVII)

wherein each subscript c is independently 0, 1 or 2, preferably each _c is ¹ ; each R4 is independently selected from H, Me, Et, (( _{CH2CH2O ) a} (C3H 6O) _b )H and mixtures thereof _; preferably, each R4 is ⁽ ( _{CH2CH2O ) a ( C3H6O} ) _b )H, wherein each subscript a is independently 1- 50, more preferably an integer of 1-25, even more preferably 1-20, 1-15, 1-10, 1-5 or even 1-2; each subscript b is independently 0-25, more preferably an integer of 0-15, even more preferably 1-5 or even 1-3, and wherein the sum of all independently selected integers of a in the leuco colorant does not exceed 100, more preferably does not exceed 80, most preferably does not more than 60, 40, 20, 10 or even not more than 5, and the sum of all independently selected b integers in the leuco colorant is at least 1 and not more than 50, more preferably not more than 40, most preferably not more than 30, 20 or even 10. 17. The leuco composition of claim 16, wherein the leuco compound has formula (CVIII)

wherein ^R8 is H or _CH3 , and each subscript b independently averages about 1 to 2.